Full text of DOI:10.1070/RC2001v070n10ABEH000646

Home Search Collections Journals About Contact us My IOPscience
State-of-the-art coordination chemistry of radioactive elements
This content has been downloaded from IOPscience. Please scroll down to see the full text.
2001 Russ. Chem. Rev. 70 865
(http://iopscience.iop.org/0036-021X/70/10/R03)
View the table of contents for this issue, or go to the journal homepage for more
Download details:
IP Address: 149.171.67.164
This content was downloaded on 10/09/2015 at 23:10
Please note that terms and conditions apply.

Russian Chemical Reviews 70 (10) 865 ± 884 (2001)
# 2001 Russian Academy of Sciences and Turpion Ltd
DOI 10.1070/RC2001v070n10ABEH000646
State-of-the-art coordination chemistry of radioactive elements
B I Kharisov, M A Mendez-Rojas
Contents
I. Introduction
865
865
867
869
870
873
874
874
875
876
877
II. General notion of technetium and actinide complexes
III. Actinide alkoxides and other oxygen-containing complexes and salts
IV. Halide complexes of actinides
V. Actinide p-complexes with allyl, cyclopolyene, arene and related ligands
VI. Hydride and hydroborate complexes of actinides
VII. Actinide complexes with macrocyclic ligands
VIII. Actinide complexes with nitrogen-containing ligands
IX. Complexes with phosphorus-containing ligands
X. Sulfur-containing actinide complexes
XI. Technetium complexes
Abstract. Modern procedures for the synthesis of coordination
and organometallic compounds of actinides and technetium and
the properties of these compounds are surveyed. Experimental
techniques, including methods for the synthesis of actinide and
technetium complexes from elemental metals (oxidative dissolu-
tion and direct electrosynthesis), salts and halide, carbonyl and
other complexes are generalised. The bibliography includes 283
references.
II. General notion of technetium and actinide
complexes
Actinium (atomic number 89) and all elements with atomic
numbers from 90 to 103 (actinides) are radioactive.17 Only four
actinides (Th ± Np) and actinium by itself were found in nature,
whereas the remaining elements were prepared artificially by
irradiation of U and other elements with neutrons or by bombard-
ment with heavy atoms. Actinides are analogues of lanthanides.
They belong to the same IIIB Group but reside in the next row.
Technetium (atomic number 43) has several isotopes two of
I. Introduction
5
Among compounds of natural and artificial radioactive elements
(Tc, Pm, Po, Fr, Ra, Ac and actinides), only organometallic
which are characterised by large half-lifes (2.12610 and
6
99m
98
1.5610 years for
Tc and Tc, respectively) and is a rhenium
compounds and complexes of technetium and actinides (An)
have been well studied. Complexes of these metals attract interest
because technetium, which is available in multikilogram quanti-
ties, is widely used for medical and technical purposes and
actinides find application in nuclear industry and power engineer-
ing. Over a period of the last two decades, a large number of
analogue.18
The electronic states of the actinide atoms and ions differ
substantially from those of the lanthanide atoms and ions. In both
series, the f level is successively filled up to the f 14 configuration;
however, this filling in actinides begins with Th only formally
because Th does not bear f electrons and is an electronic analogue
of hafnium.16 In contrast to lanthanides, actinides can exist in
various oxidation states. Actinides in the oxidation state +3 are
analogues of lanthanides, whereas actinides in the oxidation state
+4 are analogues of Hf(IV) and Ce(IV).
experimental studies, reviews and monographs were devoted to Tc
and An complexes.1
± 16
The aim of the present review is to give a
comprehensive survey of modern synthetic procedures for the
preparation of coordination and organometallic compounds of
radioactive elements. The data are systematised according to the
nature of the ligands in these complexes.
m+
m‡
Actinides produce the An
(m = 2 ± 4) and AnO2 (m = 1
or 2) ions whose highest occupied level is filled only with f
electrons. In the series of the An3+ anions, the actinide contrac-
tion is observed, this contraction changing in parallel with the
m+
lanthanide contraction. The 5f and 6d energy levels of the An
m+
ions as well as the 4f and 5d energy levels of the Ln ions
correlate with each other. The difference in the correlations for the
'
B I Kharisov Facultad de Ciencias Quimicas, Universidad Autonoma de
'
'
'
'
Nuevo Leon, 66450 San Nicolas de los Garza 18-F, Nuevo Leon, Mexico.
Fax (52-8) 374 07 09. Tel. (52-8) 375 30 68.
E-mail: bkhariss@ccr.dsi.uanl.mx
3
+
3+
An
magnetic properties and electronic spectra of their compounds.
and Ln
ions leads to the noticeable difference in the
1
7
2
6
5
2
2
6
6
1
Technetium (the 4s 4p 4d 5s or 4s 4p 4d 5s electronic config-
uration) exists in the oxidation states from +1 to +7, the
M A Mendez-Rojas Centro de Investigaciones Quimicas, Universidad
'
Autonoma del Estado de Hidalgo, Carretera Pachuca-Tulancingo
'
Km. 4.5, 42073 Pachuca, Hidalgo, Mexico. Fax (52-7) 717 20 00,
18
oxidation states from +4 to +7 being most stable.
Spin ± orbit coupling (J ) in the An
3+
ext. 5075. Tel. (52-7) 717 20 00, ext. 4881.
E-mail: mmendez@uaeh.reduaeh.mx
ions is very strong
(2000 ± 4000 cm 1) and it is *1000 cm71 stronger than J in the
7
3+
Ln ions. In contrast to lanthanides, the splitting due to spin ±
orbit coupling in actinides is comparable with the crystal field
splitting and, hence, the J value is no longer a good quantum
number. Since the 5f and 6d orbitals have close energies and the
Received 22 December 2000
Uspekhi Khimii 70 (10) 974 ± 995 (2001); translated by T N Safonova

8
66
B I Kharisov, M A Mendez-Rojas
thermally accessible excited states of actinides are filled, the
equation for the effective magnetic moment
ligands, for example, of NPh , leads to a decrease of the maximum
coordination number to 5 or even to 4. Like lanthanides, the
2
17
spherical An3+ and An
4+
ions have the highest coordination
m
e
= g[J(J + 1)]1/2
numbers (generally, 8 or 9) and often form isomorphous com-
plexes in which the polyhedron type is determined by repulsions
between the ligands (steric factors) or packing factors rather than
by the electronic effects.23 For example, the square antiprism in
is less appropriate than in the case of lanthanides.17, 19
Actinide organometallic complexes contain actinide ± carbon
p bonds, actinide ± carbon s bonds or bonds of both types.
Organometallic complexes of all early actinide elements from
thorium to californium are known.20 However, most data have
been obtained for the chemistry of organometallic compounds of
the rhodanide complexes Cs
transformed into the dodecahedron in the case of
Th(NCS) [(Me N) CO] or into the cube in the case of
(NEt An(NCS)
.17
The nature of the bond between the p-donor ligand and the
4 8 4 3 4
An(NCS) and U(NCS) (Ph PO) is
4
2
2
4
232
Th and U due to the extremely large half-lifes of natural Th and
10
4
)
4
8
238
9
U (1.41610 and 4.468610 years, respectively). The first
actinide centre has been discussed.2
4, 25
The authors emphasised
actinide organometallic compound, viz., Cp
Reynolds and Wilkinson in 1956.21
3
UCl, was isolated by
that there is no simple answer to the question as to the nature of
the bond in organoactinide complexes. Examples of almost
The actinide atoms possess rather large atomic and ionic radii
and large (up to 14) coordination numbers.22 Examples of actinide
compounds characterised by various coordination numbers and
oxidation states are listed in Table 1.
The maximum coordination numbers were found for poly-
meric uranium hydroborates, whereas the presence of bulkier
7
completely ionic binding of the Cp anions or cyclooctatetraene
(COT) with U4+ (see Ref. 26) as well as of covalent binding of the
metal atom with the aromatic ring of the ligand in uranocene
accompanied by essential ligand-to-metal electron transfer are
available in the literature.2
4, 27, 28
It was concluded
24, 29
that the
Table 1. Coordination numbers (CN) and coordination polyhedra in actinide compounds.17
Oxidation
state
CN
Coordination
polyhedron
Examples of
compounds
Oxidation
state
CN
Coordination
polyhedron
Examples of
compounds
+
7
6
6
6
octahedron
octahedron
Li
An = Np, Pu)
(NEt )(PaOCl
AnF
An = U, Np, Pu),
trans-UO Cl (OPPh
[UO Cl (acac)
PuO (C
UO
[AnO
5
(AnO
6
)
+4
8
cube
(NEt
(An = Th, Pa, U, Np)
Th(acac)
4 4 8
) [An(NCS) ]
(
bicapped trigonal
prism
4
+
4
5
),
6
bicapped
2 2 6 6
[UCl (Me SO) ](UCl )
(
octahedron
tricapped
2
2
3 2
)
] . Hacac,
) . 3 H
9
(NH
Th(tta)
Li ThF
Th(tfa)
[C(NH
U(C
An(MeCO
Na [Th(CO
An(NO
(An = Th, Pu)
(PPh )[Th(NO
An(BH (An = Np, Pu)
[An(BH
(An = Th, U)
4
)
3
(ThF
7
), LiUF
5
,
7
8
pentagonal
bipyramid
2
2
2
.
trigonal prism
monocapped
square
4
TOPO
2
2
O
4
2
O,
3
7
,
K
3
2
F
5
.
4
2 H
2
O,
hexagonal
bipyramid
Cs
2
2 2 3
(MeCO ) ]
antiprism
2
)
]
3 5
[Th(CO
3
)
3
F
3
]
(An = Np, Pu, Am),
UO )(NO (H O)
CsAnF (An = U, Np, Pu)
PaCl
.
1
0
bicapped square
antiprism
2
H
3
O
2
)
4
2 H
2
O,
(
2
3
)
2
2
2
2
)
4
(An = Th, U),
+
5
6
7
octahedron
pentagonal
bipyramid
cube
6
] . 2 H
6
3 5 2
) O
5
.
1
1
1
1
2
4
irregular
3 4 2
) 5 H O
structure
8
9
Na
An = Pa, U, Np)
(PaF
3 8
(AnF )
icosahedron
4
3 5 3 2
) (OPMe ) ],
(
4 4
)
tricapped
M
2
7
)
bicapped
hexagonal
antiprism
4 4 n
) ]
trigonal prism
(M = NH
4
, K, Rb, Cs)
.
+
4
4
5
6
tetrahedron
U(OAr)
N(SiMe
(NEt
[U(OAr)
Na
cis-UCl
trans-UBr
4
.
[
3
)
2
]
.
3
THF
] .
2 2 5
[K(THF) ] [U(NHAr)
+3
5
trigonal
trigonal
U
2
2
)
8
[Li(THF)
4
] .
bipyramid
octahedron
dodecahedron
bicapped
THF
bipyramid
octahedron
5
]
3�
6
8
6
[UCl ]
2
PuCl
6
,
.
UCl
AnBr
(An = Pu, Am, Cm, Bk),
AnI (An = Pa, U, Np, Pu)
NaPuF , AnCl
(An = U, Np, Pu, Am, Cm),
3
3 DMSO
.
4
3
2 Ph PO,
3
.
4
2 Ph
2 HMPA
(dmed)
UBr
UF
[UCl(TMPO)
3
PO,
trigonal prism
.
UCl
4
3
trigonal prism
pentagonal
U
4
3
9
tricapped
4
3
7
8
4
,
trigonal prism
bipyramid
K
3
7
.
Am(sal)
3 2
H O
monocapped
octahedron
dodecahedron
]Cl
6 3
+
0
2
6
8
framework
structure
6
Th Br12
Np(HCOO)
Th(tta) , An(S
An = Th, U, Np, Pu)
Th , An(acac)
(An = Th, U)
4
,
4
2
CNEt
2
)
4
cube
U(bipy)
4
(
square
K
7
6
F
3
4
antiprism
0
Note: acac is acetylacetonate, Hacac is acetylacetone, HMPA is hexamethylphosphoramide, dmed is N,N -dimethylethylenediamine, TMPO is
trimethylphosphine oxide, tta is thenoyltrifluoroacetonate, TOPO is tri-n-octylphosphine oxide, tfa is trifluoroacetylacetonate, sal is salicylate, bipy is
bipyridyl.

State-of-the-art coordination chemistry of radioactive elements
867
covalent binding of the metal atom with the ligand in U(COT)
involves primarily the 6d orbitals of uranium, while the 5f orbitals
are of secondary importance.
2
on the structure and stability of complexes of uranium tri-tert-
butylmethoxide was examined.42
Monomeric alkoxides can react with each other 43
As mentioned above, actinides show various oxidation states
in aqueous solutions. Stable oxidation states vary from +3 for Ac
to +6 for U and Np and then gradually decrease to +3 for Am
and the following elements, except for No (+2). For Ac, Th, Pa,
U, Md and Lr, the maximum oxidation states are stable; Np and
Pu can occur in the oxidation state +7; Am can exist in the
oxidation state +6; Cm, Bk, Cf, Es and Fm can occur in the
oxidation state +4; the oxidation state +3 is possible for No. In
aqueous solutions, virtually all actinides can exist in the unstable
6 14
C H
U(OEt)
4
+ U(OEt)
6
2
U (OEt)10 .
t
(OBut)
4 5
][U(OAr)
], were also obtained.44 Treatment of
Anionic alkoxide complexes, such as (Bu N)[U
2
9
] and
4
[Li(THF)
[U(COT)(BH
the alkoxide derivatives [U(COT)(BH
In a toluene solution of the Th(OCHPr )
i
t
4
)
2
] with alcohols ROH (R = Et, Pr or Bu ) afforded
45
4
)(OR)].
i
2
4
complex, a mono-
mer ± dimer equilibrium occurs; however, only the dimeric form
crystallises (with trigonal-bipyramidal geometry).46
Actinide alkoxides are very readily hydrolysed 17
17
2+
3+
4+
2+
oxidation state +2. The hydrated An , An , An , AnO
nsted acids. 30
2
2
‡
and AnO ions behave as Bro
È
PhMe
t
3
U
2
(OBut)
8
(HOBu ) + 2 H
2
O
2 U
3
O(OBut)10 + 7 HOBut.
Ann+ + H
An(OH)(n71)+ + H+
.
2
O
The An4+ ions are typical of actinides from thorium to
The actinide ions have large radii and, consequently, high
coordination numbers, which are often responsible for oligomer-
37, 47 ± 49
isation of homoleptic alkoxide complexes of f metals
giving rise to dinuclear (1), tetranuclear (2, 3) or higher oligo-
mers.47
4+
californium (however, U is readily oxidised). As for Th, only
Th ions exist in solutions. The acidity decreases in the series
4
+
4
+
4+
4+
4+
4+ 17
Pa 44 U > Pu > Np > Th
only in very dilute solutions. These ions tend to form polynuclear
.
Individual ions occur
species as the concentration increases
Pri
H
OPri
Ce
mAn4+ + nH
ꢀ4m� n†‡
+ nH+
O
Pri
O
2
O
An
m
(OH)n
.
i
OPri
Pr O
The acidity of the Ann+ ions depends on their charge and
radius. The An4+ and AnO2 ions are much stronger acids than
Ce
i
O
OPri
Pr O
2‡
i
OPri Pr
O
the An3+ and AnO2 ions, respectively.17 The redox behaviour of
actinides is complicated by their high radioactivity, which, in
particular, results in the formation of hydrogen peroxide in
aqueous solutions.
‡
Pri
H
1
Py
RO
RO
OR
OR
Th
R
O
O
R
RO
The data on the complex formation of the actinide ions An3+,
Th
OR
Nd
An4+, AnO and AnO (An = U, Np or Pu) with chlorides were
‡
2‡
R
OR
Th
Nd
2
surveyed in several comprehensive reviews.
2
RO
RO
O
OR
OR
Th
30 ± 32
The results of
,
OR
RO OR RO
2
2
‡
R
O
O
recent studies of hydrated and chloride complexes of UO
NpO2 , Np , Pu , etc. by XAFS (X-ray absorption fine
OR R RO
RO
OR
OR
+
4+
3+
Nd
Nd
O
R
OR
structure) spectroscopy were covered in Refs 33 and 34. In
particular, using hydrated ions and fluoride complexes of U(IV)
and Th(IV) as examples, it was demonstrated that the coordina-
tion number of these hydrated ions is 10 and the M7O distances
for U(IV) and Th(IV) are in the ranges of 2.42 Æ 0.01 and
RO
Py
2
(R = Pri)
3 (R = CH Bu )
2
t
Dimeric actinide complexes are exemplified by the
{U[O(2,6-Pr C H } complex (4), which contains the unusual
6 3 3 2
i
)]
2
ꢀ
34
2
.45 Æ 0.01 A, respectively. The results of physical and chemical
p-arene bridge and is sterically hindered due to the presence of the
studies of hydrated complexes of uranium were published in the
literature.3
isopropyl groups.4
7, 49
interactions both in the solid state and in solution.
This complex is stabilised through p-arene
5, 36
Mo
È
ssbauer spectroscopy is very convenient to use for studying
the oxidation states and the symmetry of the ligand environment.
Pr
Pr
i
i
ArO
ArO
O
232
231
238
240
The Mo
243
È
ssbauer effect is observed for Th, Pa, U, Pu,
237
M
Np generated upon the 237U
Am and, particularly,
7
71
b -decay. The maximum isomer shifts (up to 770 mm s ) are
observed for Np(VII) compounds; for Np(III) compounds, these
shifts decrease to +30 mm s7 (see Ref. 37).
Pri
M
OAr
OAr
1
O
Pri
III. Actinide alkoxides and other oxygen-
containing complexes and salts
4
i
2
Ar = 2,6-Pr C H ; M = La, Nd, Sm, Er, U.
6
3
Uranium alkoxides are similar to alkoxides of transuranium
elements. Their chemistry has been surveyed in the recent
Some actinide complexes can occur both in the monomeric
and dimeric forms. Thus treatment of metallacycle 5 with iso-
review. 37 Homoleptic alkoxides An(OR)
are known for n = 3
U and Pu), 4 (Th, U, Np and Pu), 5 (Pa and U) and 6 (U). A great
propyl alcohol afforded the homoleptic Th
i
(OCHPr )
complex.
n
2
2
8
(
SiMe
N
3
quantity of such U and Th compounds are available, whereas only
a few Pa and Pu complexes were prepared. Alkoxides of uranium
in the the oxidation states +3, +4, +5 and +6 are known.
Complexes characterised by mixed oxidation states, such as
(Me Si) N
3
2
i
Th
SiMe2
+ 4 HOCHPr2
(Me Si) N
3
2
[
U(OPh)
3
(THF)]
2
[UO
2
(THF)
2
]
2
(m-OPh)
4
(m
3
-O)
2
, were also pre-
5
pared.38 Compounds of U(IV) are analogous to Th(IV) com-
pounds.
i
1
2
2 8 3 2
/2 Th (OCHPr ) + 3 HN(SiMe )
6
Most actinide alkoxides are oligomeric {like [U
However, derivatives of bulky alcohols and 2,6-disubstituted
phenols are monomeric,17 for example, U(OCHBu )
3
O(OBut)10]}.
In the solid state, the latter exists as dimer 6 (the coordination
number of thorium is 5) consisting of two ThO fragments (with
trigonal-bipyramidal geometry), which are linked via a shared
t
2
39
4
,
5
U(OEt)
6 3
Ar = 2,6-Bu C H ).
5
,37 U(OMe)
6
,
37, 40, 41
U
2
(OEt)10
The influence of electronic factors
,
U(OAr)
4
and U(OAr)
3
t
(

8
68
B I Kharisov, M A Mendez-Rojas
axial-equatorial edge.44 At room temperature, this complex in
The corresponding thorium derivatives can also be prepared
by alcoholysis of alkyl complexes, for example, of Cp ThMe , the
non-coordinating solvents exists as monomer 7.4
6, 47
Ã
2
2
Ã
reactions of Cp ThCl
2
2
with alkali metal hydroxides, the insertion
37
i
i
Th
2
(OCHPr )
8
2 Th(OCHPr )
4
2
2
of ketones at the Th7Alk bond (see the review and references
cited therein)
6
7
PhMe
(OPri)
(HOPri)
Ã
Ã
The dimeric halide-alkoxide complex Th
2
I
4
4
2
Cp2ThCl(Me) + Me
2
CO
Cp2ThCl(OCMe
3
) ,
was prepared by the reaction of metallic thorium with 2 equi-
valents of iodine in isopropyl alcohol.50 This reaction provides an
example of the direct synthesis from elemental metals. The
2
37
and hydrogenation of Z -acyl complexes
H
2
i
i
Ã
2
But)
Ã
2
But).
Th
group Pꢁ) has a bioctahedral structure (the octahedra are linked
2
I
4
(OPr )
4
(HOPr )
2
complex (the triclinic system, space
Cp2ThCl(Z -OCCH
2
2 2
Cp2ThCl(Z -OCH CH
1
via a shared edge), the isopropyloxy anions occupying the bridging
Crystallisation of a Pu(IV) salt (0.15 mol litre71) from a
solution of Na CO (2.6 mol litre ) afforded single crystals of
2 3
[Na Pu(CO ) ] Na CO 33 H O (the space group is P2 /c). In
6 3 5 2 2 3 2 1
the solid state, the asymmetric unit contains a complex framework
7
1
positions. This complex is isostructural to its uranium analogue
i
i
50
.
.
61
U
2
I
4
(OPr )
4
(HOPr )
2
(see Ref. 51) and is structurally similar to
a number of alkoxide and halide-alkoxide compounds of lantha-
i
i
67
+
nides and early transition metals, such as M
2
(OPr )
(R = CH CH
]I intermediates
8
(HOPr )
2
consisting of [Pu(CO
3
)
5
]
anions and Na cations linked
through interactions between the CO3 ligands and the H O
M = Zr or Ce) 52 and Ti
It was assumed that the [AnI(OPr )
Cl
(OR)
(HOR)
i
Cl).53
2�
(
2
4
4
2
2
2
2
(HOPri)
molecules. The [Pu(CO
)
]
67
5
anion can be considered as a
2
4
3
(
An = U or Th) were initially formed, which then underwent
0
pseudohexagonal bipyramid with three carbonate ligands in the
equatorial plane and two carbonate ligands in the axial positions.
Its structural unit is very similar to that of the related
dimerisation.5 Other alkoxide complexes of actinides, for exam-
(OBut)
(HOBu ), (TBA)U
55
t
54
(OBu )
t
(TBA is tetrabutyl-
ple Th
ammonium) and KU
demonstrated that the K+ cations in the latter complex in
solutions remain associated with the dimeric anions, the structures
of the molecular unit in the crystalline state and solution being,
apparently, identical.
2
8
2
9
(OBut)
,
were also characterised. It was
[Th(CO
Na
Ref. 61 and references cited therein). Clark et al. believed that
)
]
67
anion involved in the crystal structures of
2
9
3
5
6
3 5 2 2 3 6 3 5 2
[Th(CO ) O and [C(NH ) ] [Th(CO ) ] 4 H O (see
] . 12 H
.
61
the well-known coordination polyhedron (hexagonal bipyramid)
4
7
62 ± 64
in the [PuO
7
3 5
the [Pu(CO ) ]
2
(CO
3
)
3
]
anion (13).
complex (12)
is analogous to that of
6
Oxidation of the uranium(III) aryloxide complex U(OAr)
OAr is 2,6-di-tert-butylphenoxide) afforded various oxide and
3
(8)
O
(
halide-oxide complexes of U(IV).
50
O
O
O
O
O
a
e
O
O
FUIV(OAr)
U(OAr)
ClUIV(OAr)
U(OAr)
BrUIV(OAr)3
O
O
O
3
O
Pu
O
O
b
c
d
f
O
Pu
I
2
2
U(OAr)
(ArO) USU(OAr) (10)
3
3
3
O
O
O
g
h
O
O
O
O
O
8
IUIV(OAr)
O
O
3
3
12
4
(ArO) UOU(OAr) (9)
3
3
O
13
(
(
a) AgBF
4
or AgPF
6
; (b) CI
4
; (c) PCl
5
; (d) O
2
; (e) AgBr, CBr
4
5
or PBr ;
f) COS or Ph
3
P=S; (h) N
2
O, NO, Me NO or pyridine N-oxide.
3
The structure of yet another carbonate complex, viz.,
.
(
Me
4 4 2 3 3 2
N) [NpO (CO ) ] 8 H O, consists of alternating anionic
65
In the presence of an appropriate source of chalcogenide,
oxidation gave rise to bridged binuclear uranium(IV) complexes 9
or 10.50
Alkoxide complexes of cyclooctatetraenyluranium(IV) were
synthesised by the reactions of cyclooctatetraenyluranium pre-
cursors with alcohols.56
and cationic layers. The water molecules of crystallisation are
involved in the formation of the {[NpO
.
4n�
n
2 3 3 2
(CO ) ] 8 H O}
anionic layers. Analogous uranium and uranyl complex ions in
70
66, 67
68
69
70
carbonate,
sulfate, nitrate, phosphate, silicate and
citrate complexes 71 as well as in other oxygen-containing com-
pounds were also studied. In particular, the behaviour of carbo-
�
The unusual monomeric complex U(OTeF
5
)
6
can be consid-
nate complexes of uranium in CO
2
± HCO3 solutions of various
71
ered as an analogue of metal alkoxides.57 In spite of the large
molecular weight, this complex sublimes at 333 K (1.3 Pa).57
Actinide alkoxides are generally prepared from dialkylamides
4
ionic strengths (I = 0.5, 1.0, 2.0 or 3.0 mol litre of NaClO ) at
65
25 8C was examined by UV/Vis spectrophotometry. The
authors believed that tetracarbonate complexes exist in an equili-
brium with pentacarbonate complexes
and alcohols.44 The homoleptic UX
(MeCN) complex can serve
4 n
as a precursor in the synthesis of mixed halide-alkoxide com-
pounds of uranium. The coordination environment in the reaction
product depends on the nature of the halogen. Thus the reaction
3 5
[U(CO ) .
]67
[
U(CO
)
4
]47 + CO3
2�
3
Citric acid forms mixed Fe and U complexes analogous to the
citrate complex of uranium. The mixed Fe ± U citrate complex is
71
stable to biodegradation.
Among other oxygen-containing actinide compounds, ura-
nium peroxo complexes with various ligands, viz., with tri- and
tetradentate Schiff's bases,72 amines or aminocarboxylic acids,
were described. The einsteinium(II) complexes with crown ethers
2
[Es(18-C-6)]L (L = ClO4 and BF , BPh ) were prepared. The
behaviour of einsteinium(II) in THF was examined by co-crystal-
lisation. It was found that the coefficients of co-crystallisation of
of UBr
the Br U(OAr)
the anionic [K(THF)
4
(MeCN)
(THF) 4THF complex, whereas UCl
][UCl (OAr) ] complex. In solution, mixed
4
with 2 equivalents of KOAr in THF afforded
.
2
2
4
produced
4
3
2
halide-aryloxide complexes do not undergo ligand exchange.
Light halides of uranium(IV) are reagents of choice in the meta-
thesis because UI (MeCN)
4 4
is thermally unstable.58 A series of
73
� � �
74
aryloxides and alkoxides of (triamidoamine)uranium(IV) were
described.59
One of the approaches to the synthesis of methoxide deriva-
4 4
Ã
Ã
�
tives of actinides of type 11 involves the reactions of Cp MH
2
2
(Cp
is pentamethylcyclopentadienyl; M = U or Th) with trimethyl
phosphite in pentane.60
Es(II) with solid [Sr(18-C-6)]I
BF ions as additives and are independent of the presence of the
2
in THF depend on the ClO4 and
�
4
�
BPh ions.
4
Very stable actinide complexes with b-diketones [for example,
with An(acac) or AnO (acac) ] are used for isolation and
separation of actinides by extraction. These complexes are pre-
pared by the reactions of metal or actinyl halides with the
P(OMe)
3
Ã
Ã
Ã
2
Cp ThH
2
2
Cp Th(OMe)
2
2
+ [Cp Th(OMe)
2
](m-PH)
4
2
2
7H
2
11

State-of-the-art coordination chemistry of radioactive elements
869
Table 2. Preparation of actinide alkoxides and related oxygen-containing
complexes.
O
U
O
O
O
O
O
Starting
compound
or metal
Reaction
system
Products
Ref.
1
4
Synthesis from elemental metals
U anode Hbac,
or N
Hacac,
or N
Based on the data on the electronegativities obtained earlier
see references cited in the study 78), the U7O bond orders in the
complexes 14, UO (acac) , UO (Hdbm) and UO (HBTF)
2 2 2 2 2 2
UO
UO
2
(bac)
(bac)
2
2
(Hbac)0.5
,
84
84
(
O
2
2
2
(see a)
(see a)
2
U(acac)
4
,
(Hdbm is dibenzoylmethane, HBTF is 1,1,1-trifluoropentane-
2,4-dione) were calculated. The results of the calculations indi-
cated that the equatorially coordinated 2-hydroxy-1-naphthalde-
hyde ligand exerts a pronounced effect on the oxygen atoms of the
.
O
2
UO
2
(acac)
2
Hacac
Synthesis from salts
UO
2
(MeCO
2
)
2
Hacac
Hdbm
UO
UO
UO
2
(Hacac)
2
(Hdbm)
2
(HBTF)
2
2
2
75 ± 77,
85
2‡
78
UO anion.
2
77
Based on the spectra of neptunium b-diketonates, the
Np(IV) complexes with acetylacetonate, dibenzoylmethane, ben-
zoylacetone (Hbac), benzoyltrifluoroacetone (Hbtfa) and the-
noyltrifluoroacetone (Htta) can be divided into two groups
according to the type of coordination polyhedron about the
HBTF in EtOH
i
i
Th(OPri)
Pa(OEt)
Np(OR)
(HOPri)
ThCl
PaCl
NpCl
4
NaOPr , HOPr
4
x
37, 38, 86
37, 87
5
NaOEt, EtOH
LiOR, ROH
5
4
4
37, 88
central atom. In Np(acac)
nation polyhedron is a tetragonal antiprism, whereas Np(bac)
and Np(btfa) (dbm is dibenzoylmethanate, bac is benzoylaceto-
4 4 4
, Np(dbm) and Np(tta) , the coordi-
(
R = Me, Et)
Synthesis from halide complexes
UBr (MeCN) KOAr
4
4
U(OAr)(THF) .
nate and btfa is benzoyltrifluoroacetonate) have bitetrahedral
structures. Apparently, when Np(IV) b-diketonates are dissolved
in benzene, the bidentate ligands are oriented about the central
atom so that the oxygen atoms form the tetragonal-pyramidal
4
4
Br
2
89
(
THF)
4
t
2
ThBr
4
(THF)
4
2,6-Bu C
see b)
6
H
3
OK
ThBr
2
(OAr)
2
(THF)
2
44, 90
91
(
77
coordination.
Py
2
PuCl
6
NH
3
, PhH,
Pu(OPri)
Pu(OPri)
4
,
It should be noted that uranium b-diketonates were also
prepared by direct electrochemical synthesis using a dissolving
anode. Thus electrochemical oxidation of uranium in the presence
i
Pr OH c
4
(Py)
Synthesis from b-diketonates or alkoxides
t
of b-diketones afforded chelate complexes of the UL
or UO
The reaction with benzoylacetone
gave rise to a compound with composition UO (bac) (Hbac)0.5
2 2
L
CHBu2
4
Me
U
1 ± 83
t
type (L is diketonate).8
Bu2HCO
O
t
U(OCHBu )
4
MeLi
t
92
93
2
Bu HCO
Li
O
2
2
2
along with the above-mentioned complexes.82 In our opinion, the
structure 15, which was assigned to this compound on the basis of
the IR spectroscopic data, needs further investigation.
t
CHBu2
Th(acac)
4
electrochemical
reduction d
[Th(acac)
4
]7
Ph
Me
Me
Ph
Synthesis from p-complexes
O
O
O
O
O
O
(MeCp)
3
U(THF) alcohols or
(MeCp)
(R = OMe, OPri,
OPh, SPri)
3
UR
94, 95
O
2
U
O
C(Ph)CH
2
C(Me)
O
U
O
2
O
thiols
O
Ã
Ã
Cp UH
3
EtOH
Cp UOEt
3
96
96
Me
Ph
Ph
Me
1
5
HU(C
5
5
H
H
4
But)
SiMe
3
EtOH
EtOH
(C
5
5
H
H
4
But)
SiMe
3
UOEt
Selected methods for the synthesis of actinide alkoxides are
listed in Table 2.
HU(C
4
3
)
3
(C
4
3 3
) UOEt 96
a
Direct electrochemical synthesis; b alkylation of the product afforded
Th(OAr)
rise to Pu(OPri)
known Th(III) complexes are few in number.
2
(CH
2
SiMe
3
)
2
; c recrystallisation from hot isopropyl alcohol gave
IV. Halide complexes of actinides
(HOPri); d the product lost acac to form Th(acac)
7
; the
4
3
Light actinides (U, Np and Pu) react with iodine or bromine in
7, 98
donor solvents 9
AnX L (X = Br or I).
to give complexes of trivalent actinides
3 4
corresponding diketone in the presence of a base. In the case of
An(IV) actinides, only fluorine-containing diketonates form com-
0
8C
U + 1.5 I
2
+ n L
UI
3 n
L
2
plexes with Lewis bases; diketonates of actinyls AnO (An = Np
16a ± c
or Pu) generally exhibit the Lewis acid properties and are
stabilised through the formation of adducts. The fluorinated
complex UO (hfa) (hfa is hexafluoroacetylacetonate) exhibits
n = 2, L = DME (a); n = 4, L = THF (b), Py (c).
2
2
This reaction is a convenient and highly efficient procedure for
the preparation of halide complexes of actinides in quantitative
yields, which does not require special equipment.
Complexes of uranium triiodide with Lewis bases are used as
intermediates in the synthesis of other trivalent uranium com-
pronounced acidic properties and its adducts with water and
alcohols can be sublimed without decomposition.
17
Uranyl acetylacetonate,7
5, 76
other actinide b-diketonates
77
78
and uranyl complexes with 2-hydroxy-1-naphthaldehyde (14)
and 2-hydroxybenzaldehyde 79 were studied in detail by spectro-
scopic methods. These investigations made it possible to establish
the structure of the complex 14 synthesised previously.80
pounds. For example, the UI
prepared in large amounts, is a soluble form of UI
subsequent use in synthesis. Reactions involving solvate com-
plexes of other uranium halides or alkoxides can be complicated,
for example, by the formation of mixtures of products.
(THF)
adduct (16b), which can be
convenient for
3
4
3
98

8
70
B I Kharisov, M A Mendez-Rojas
The mononuclear complex UI
space group P2 /c. The coordination environment about the
3
(THF)
4
(16b) crystallises in the
give rises 97 to
uranium(IV)
a
mixture of
derivative,
a
viz.,
U(III) complex and
the metallacycle
1
a
central U atom is a pentagonal prism. The complex 16b is stable
up to 75 8C. At a higher temperature, the THF molecules are
2 3
Si) N] U(CH SiMe NSiMe
).107
[(Me
3
2
2
2
successively eliminated; at 162 8C, UI
Other adducts of uranium halides UX
3
is finally formed.
Selected procedures for the synthesis of halide complexes of
actinides are listed in Table 3.
3
were also
described.99 ± 103
Actinide tetrahalides readily react with Lewis bases to give
Table 3. Synthesis of halide complexes of actinides.
complexes containing two or four donor atoms. The compositions
.
of some resulting products differ from usual AnCl
.
4
2 L or
n L complexes, where
Starting
compound
or metal
Reaction
system
Products
Ref.
.
AnCl
n = 2.5,
4
4 L. For example, the AnCl
4
5
[L is N,N-dimethylacetamide (DMA)] or 6
L = DMSO or TMPO), were prepared. Complexes with compo-
(
sition AnCl
The coordination polyhedron typical of the AnCl
.
17
4
2 HMPA (An = Th or U) are extremely volatile.
.
Synthesis from elemental metals
4
2 L complexes
U
X
2
(X = Cl, Br, I), UX
THF
(X = Br, I),
THF
Br , MeCN
HgCl , THF
or I
THF
Synthesis from salts or halide complexes
3
(THF)
4
97, 98
is a trans-octahedron.17
The cationic uranium(IV) complexes UX
I; L is a bulky neutral O-donor ligand, such as tris(pyrrolidin-1-
2 4 2
L Y [X = Cl, Br or
Th
X
2
ThX
4
(THF)
4
44
4 4
or BPh
] were described.1
02
yl)phosphine oxide; Y = ClO
The reactions of UI with a series of sulfoxide donor ligands in
non-aqueous media were investigated. The behaviour of UI was
compared with that of UCl and UBr in the presence of the same
ligands. It was demonstrated that UI was readily oxidised with
dimethyl or diisobutyl sulfoxide at *20 8C. Only complexes with
compositions UI (DMSO) and UI (DIBSO) (DIBSO is diiso-
butyl sulfoxide) appeared to be stable and were isolated.
Th anode a
4
2
ThBr
UCl (THF)
AnX (THF)
4
(MeCN)
4
108
109
97
4
(see b)
U
2
4
3
4
4
An (U, Np, Pu) Br
2
2
,
3
4
(see c)
4
4
8
4
6
1
04
UI
4
DMSO
UI
n = 6, 8)
UI (DIBSO)
4
(DMSO)
n
104
104
All actinide halides tend to accept Hal7 ions to form anionic
complexes. The stability of the complexes decreases in the series
F 44 Cl > Br 44 I. Adducts of actinide trihalides are ionised to
(
DIBSO
4
n
(
n = 6, 8)
a large extent. Thus uranium trichloride crystallises from dimethyl
.
.
UCl4
NaH
UCl3 n THF
44
sulfoxide as the solvate UCl
the dodecahedral [U(OSMe
3
3 DMSO. Its structure consists of
+
)
8
]
cations and the octahedral
anions. X-ray diffraction study demonstrated that ameri-
cium chloride hexahydrate has an ionic structure built of the
.
2
ThBr
4
(THF)
(THF)
4
4
KNPh
2
, THF
Th(NPh
2
)
4
THF
110
7
[
UCl ]
6
KNMePh, THF
Cp*MgBr(THF)
KCp*, THF
K[Th(NMePh)
5
]
ThBr
4
Cp*ThBr (THF)
3
3
111
+
7
[
AmCl
linked via hydrogen bridges.
Uranium and protactinium pentahalides generate complexes
2
(H
2
O)
6
]
cations and [Cl(H
2
O)
6
]
anions, which are
17
UI3(THF)4
Cp*UI (THF)3
20, 98
97, 112
2
AnI
An = U,
Np, Pu)
3
(THF)
4
NaN(SiMe
THF
3
)
2
,
3 2 3
An[N(SiMe ) ]
.
of the AnX
Dissolution of UO
adduct, whereas dissolution of Pa(V) hydroxide gave rise to the
ionic complex (SO)(PaCl . Generally, actinide hexahalides do
not react with Lewis bases (except for the UCl
whereas actinyl halides readily form complexes with composition
5
L type (X = Cl or Br; L = R
3
PO or HMPA).
(
.
3
in thionyl chloride afforded the UCl
5 2
SOCl
a
Direct electrochemical synthesis; b a large amount of a uranium amalgam
6 2
)
was obtained as a by-product; c air-sensitive.
.
6
bipy complex),
.
17
AnO
2
X
2
n L (n = 1, 1.5, 2, 3 or 4).
and UF
Uranium fluorides UF
5
6
give complexes with 2-fluo-
ropyridine (F-Py) or bipy. Thus UF in CH Cl produced the
12 bipy complexes, respectively. However,
in the case of the UF ± bipy system, reduction of UF was the
predominating process and the formation of U 12 bipy {the
authors believed that this complex has the structure
105
6
2
2
V. Actinide p-complexes with allyl, cyclopolyene,
arene and related ligands
.
.
4 2
UF (F-Py) and U F
6
6
.
2
F
Considerable recent attention has been given to actinide com-
plexes with allyl, cyclopolyene and arene ligands, particularly,
20
with cyclopentadiene and its derivatives (see review ).
2
+ .
�
.
[
UF
stage of this reduction.
In the case of UF , two products were obtained and structur-
ally characterised. These are the extremely moisture-sensitive
4
(bipy)
2
]
[UF
7
]
UF
6
} can be considered as the first
2
Allyl complexes can be synthesised from AnCl
Grignard reagent 44
4
and the
5
Et
2
O
3
.
+
7
AnCl + AllMgCl
4
4
An(Z -All) .
UF
5
bipy and the ionic derivative [(bipy) H] [UF
The AnX (THF) complexes serve as synthetic precursors of a
2
6
] .
<
0 8C
3
4
number of inorganic and organometallic complexes due, in
particular, to their high solubility in toluene and THF. The use
According to the data of low-temperature NMR spectro-
scopy,20 the allyl groups in these complexes are Z -coordinated
3
of UI
synthesis of many other compounds of trivalent uranium.
Salts of organic ligands with alkali metals react with
AnX (THF) to give the corresponding aryloxides, amides, etc.
3
(THF)
4
can also provide a convenient approach to the
and can be replaced under the action of HX or alcohols to
44
97
produce, for example, U(C
3
H
5
)
3
X or [U(C
the dimeric tert-butyloxyallyl complex [U(C
3
H
5
)
3
(OR)]
2
.
Thus
(OR)] (17) was
3
H
5
)
3
2
synthesised.20
3
4
This reaction can serve as a highly efficient procedure for the
preparation both of the known and new complexes of trivalent
actinides. Thus reduction of uranium tetrachloride with NaH or
OBut
But
O
U
106
Na/Hg in THF afforded poorly soluble UCl
3
(THF)
n
.
This
U
O
compound is sometimes used for the synthesis of other uranium
complexes. However, this procedure is of limited application
due to the formation of by-products. For example, the synthesis
But
OBut
1
7
3 2 3 3 n 3 2
of U[N(SiMe ) ] from UCl (THF) and NaN(SiMe ) often

State-of-the-art coordination chemistry of radioactive elements
871
Of actinide p-complexes, the uranium(III, IV) and
thorium(III, IV) complexes with cyclopentadiene and its deriva-
tives were obtained in the widest range.
Uranium(V, VI) complexes and neptunium(VI) and califor-
nium(III) sandwich complexes were also prepared.44 These com-
plexes can be compositionally divided into the following groups:
between the 5f orbitals of U and the 2p orbitals of CO, which leads
Some
to stabilisation of the 5f atomic orbitals of uranium.2
0, 119
uranium complexes containing carbonyl ligands were described in
20
120
the study. The relativistic effective core potentials of tris(cyclo-
pentadienyl) actinide complexes were calculated by the ab initio
quantum-chemical method. These complexes were examined also
by gas-phase UV photoelectron spectroscopy.
121, 122
Cp
and CpAnX
ing cyclopentadienyl alkyls, carbonyls, alkoxides, etc. are also
known.20 All Cp
An complexes are poorly soluble in organic
solvents. The U7C distances in the Cp
n
An (n = 3 or 4), Cp
n
AnX (n = 2 or 3), Cp
2
AnX
n
(n = 1 or 2)
1
n
(n = 2 or 3), X being generally Hal. The correspond-
3 2
The Cp AnR complexes tend to incorporate the CO, CO
2
2
2
and CNR ligands to form Z -acyl (18), Z -carboxylate (19) and
2
20
4
Z -iminoalkyl (20) complexes, respectively.
ꢀ
U complex are 2.81(2) A.
4
R1
R1
O
The bonds between the An atom and the ligand are covalent in
character.20, 44
C
AnCp
3
C
AnCp3
1
R C
AnCp
3
O
N
O
3
The Cp An complexes are strong Lewis acids and form
complexes with various Lewis bases (see Ref. 24 and references
cited therein).
R2
1
8
19
20
The Cp
actinide compound,
containing the non-bridging metal ± metal bond between, for
example, uranium and iron or ruthenium [Cp U7MCp(CO)
M = Fe or Ru] or between uranium and germanium
3
UCl complex, which was the first synthesised organo-
The Cp
U7Sn or U7Ge bonds were prepared from Cp
replacement of the chloride ligand.24 In the crystal structures of
Cp U(OPh) and Cp U(OSiPh ), which were established by X-ray
3
UX compounds containing the U7P, U7N, U7Si,
21, 44
serves as a precursor of compounds
3
UCl by the
3
2
,
3
3
3
diffraction analysis, the U7O distances are shortened [2.119(7)
).2
0, 113
The first organouranium(III) com-
viz., tris[(cyclopentadienyl)uranium] and some
its derivatives of the Cp UL type, are also used for the synthesis
and 2.135(8) A, respectively] and the U7O7C and U7O7Si
ꢀ
(Cp
plexes,
3
UGePh
2
3
4, 114, 115
angles are 159.4(5) 8 and 172.6(6) 8, respectively. These geometric
3
parameters are indicative of strong p-bonding between the U and
of bimetallic compounds.24
O atoms in oxygen-containing uranium complexes.
24
The
bimetallic oxygen-bridged complex, viz., m-O-bis[tris(cyclopenta-
dienyl)uranium(IV)] was investigated. The absolute enthalpies
of the cleavage of the uranium ± ligand bonds in complexes
a
123
Cp U=N
3
N=UCp3
n
containing the U7S bonds of the L
SiMe or C SiMe ; R = Et or Bu) were determined.
The heteroatomic compound UCp (m-Cl) Li[(Me NCH CH
3
U7SR type (L = C
5
H
4
Bu ,
b
c
d
124
C
5
H
4
3
9
H
6
3
Cp U=N
3
N=UCp3
)
2
.
2
2
2
2
2
.NMe] containing two chloride bridges provides yet another
25
Cp UO
3
C
C
UCp3
NPh
UCp3
example of bimetallic complexes.1
The electronic structure and configuration of the ground state
Cp US
3
of
the
monomeric
alkyl
uranium(III)
The ground state of the
complex
Ã
126
Cp U(THF)
3
S
Z -Cp UCH(SiMe were studied.
molecule is 4A [(a ) (a ) (a ) ], which corresponds to the 5f
configuration of the uranium atom; its energy is close to that of
5
3 2
)
2
00
0
1
00
1
00
1
3
e
f
Cp UTeUCp3
3
00
2
1
Cp USUCp3
3
the higher-lying 4A (5f 6d ) state. The uranium(III) ions free of
3
ligands can adopt two different electronic configurations, viz., 5f
2 1
g
h
3
Cp USeUCp3
and 5f d (see Ref. 126 and references cited therein). The ground
state of the U3+ ions in the gaseous phase has the 5f config-
uration. According to the results of an EPR study of the
3
R
N
5
Cp U
2
UCp2
Th[Z -C
H
the ground state adopts the 6d configuration, whereas the free ion
(SiMe
)
]
3
complex in the gaseous state, Th(III) in
1
5
3
3
2
N
R
1
127
has the 5f configuration.
The insertion of CO or CO
Cp AnR
into the An7R bond in the
2
complexes gave rise to complexes 21 ± 23 or carbene-like
(
(
a) 1,4-(N
f ) COS or Ph
3
)
2
C
6
H
4
; (b) 1,3-(N
3
)
2
C
6
H
4
(c) PhNCO; (d ) CS
2 3
; (e) TePBu ;
2
Ã
3
P=S; (g) Ph P=Se; (h) Cp
3
3
U=NR; R=Ph, SiMe
3
.
2
2
Ã
20, 128 ± 130
Z -acyl complexes Cp An(COR)
2
(24, R = Alk).
2
Voltammetric studies 116 demonstrated that oxidation of
(RC UCl (R = H, Me, Bu or Me
disproportionation. NMR studies revealed electron transfer and
R
R
R
t
5
H
4
)
3
3
Si) was accompanied by
O
O
O
R
R
or Alk).2
4, 117
O
O
O
O
ligand exchange in Cp
3
UX (X = Hal, BH
4
Ã
Ã
Cp2An
Ã
Ã
AnCp2
AnCp2
Cp2An
�
e
�
Cp
3
UX
Cp
3
UX ,
O
R
O
�
O
R
�
UX + Cp
e
2 3
22 (R = CH SiMe )
Cp
3
3
3
U*(THF)
Cp
3
3
U*(THF) + Cp U*X,
R
�
�
Cp
UX + Cp
3
U*(THF)
Cp
3
U*(THF) + Cp
3
U*X .
21 (R = Me)
23 (R = Me, Bn)
The equilibrium constants of the ligand exchange in com-
plexes with substituted cyclopentadienyl ligands were deter-
O
R
R
mined. 2
MeCp)
P(OMe)
CO, whereas binding of (Me
4, 118
It was found that binding of ligands with
Th
(
3
U is reduced in the series of the ligands PMe
> Py > tetrahydrothiophene > THF> quinuclidine >
SiC U with the EtNC ligand is
3
>
3
O
3
5 4 3
H )
stronger than with the EtCN ligand, which is indicative of
substantial p-back bonding with uranium in the case of p-acceptor
ligands.24 The results of calculations of the electronic structure of
24
3
the model Cp U(CO) complex showed substantial back bonding

8
72
B I Kharisov, M A Mendez-Rojas
3 2
The dynamic behaviour of CpUCl L in solutions was exam-
ined.24, 131 In toluene, rapid isomerisation and the ligand exchange
P
BH
4
4
were observed.24
4 4
C Me PK
U
4 4
U(BH )
BH
P
Cp
U
Cp
U
Cl
Cl
Cl
L
L
Cl
,
26
Na/Hg
Cl
L
TeBH
4
L
Cl
Cp
U
Cp
U
Cp
U
P
Cl
Cl
Cl L*
L
Cl
7 L
L
Cl
L*
.
L
7 L* Cl
L
L
Cl
L*
P
U
BH
P
Nu
4
BH
4
C
4
Me
4
PK
L
Cl
Cl
ArU(BH4)3
U
P
Nu
BH
4
U
P
3 3
The tribromide complex Cp*ThBr (THF) (see Ref. 111 and
2
8
Table 3) is a convenient compound for studying the chemistry of
mono(pentamethylcyclopentadienyl) derivatives of thorium.
Treatment of this complex with bases or Grignard reagents
afforded aryloxide or alkyl derivatives.1
P
2
7
Nu = THF, OPPh
3
.
11
The structure of the first cycloheptatrienyl sandwich complex
[K(18-C-6)][U(Z-C
that the cycloheptatrienyl ligand can be formally considered as
THF
35
7 7 2
H )
] was established.1 The authors believed
Cp*ThBr
3
(THF)
3
+ KOAr
Cp*ThBr
2
(OAr)(THF) + KBr,
1
8 h
3�
THF
C
+5.
7
H
and the uranium atom occurs in the oxidation state
7
Cp*ThBr
Cp*ThBr
3
2
(THF)
3
+ 2 KOAr
Cp*ThBr
2
(OAr)
2
2
+ 2 KBr,
1
35, 136
1
8 h
7 7
It was demonstrated that the C H ligands in this
compound are planar and are located parallel to each other and
perpendicular to the axis passing through the uranium atom and
the centres of the rings.1
(OAr)
2
+ MeMgBr
Cp*MeTh(OAr)
+ MgBr
2
.
35
In 1971, the first indenyl derivative of actinides was prepared
upon treatment of uranium tetrachloride with indenyl anions.132
Generally, cyclooctatetraene complexes of actinides have the
composition (COT) An or (COT)AnX (X = Hal). Compounds
2 2
The indenyl uranium(III) complex U(C
9
H
7
)
3
was synthesised from
of the mixed type (COT)AnCp can also be obtained. Some of these
20
33
and indenylsodium.1 Indenyl actinide(IV) complexes 25
UCl
were prepared from the corresponding halides and indenylpotas-
3
complexes contain solvent molecules, for example, THF. Com-
pounds of this type can be prepared, for example, according to the
following procedures:
sium.20
X
AnCl
4
+ 2 K
2
(COT)
2
An(COT) + 4 KCl ,
K(C
9
H
7
)
U
An = Th, Pa, U, Np;
AnX
4
THF
(
PyH)
ThCl
UCl
Cyclooctatetraene complexes of uranium, thorium, protacti-
2
PuCl
+ Th(COT)
+ COT + 2 NaH
6
+ 2 K
2
(COT)
2 (COT)ThCl
(COT)UCl
Pu(COT)
(THF)
(THF)
2
+ 4 KCl + 2 PyHCl ,
4
2
2
2
,
25
4
2
2 2
+ 2 NaCl +H .
An = Th, U, Np; X = Hal.
Uranium complexes 26 ± 28 containing phosphacyclopenta-
dienyl ligands were described.24, 134
nium, neptunium and plutonium [(Z-COT)An(m-SPr)
2
]
2
with
Table 4. Selected actinide complexes with allyl, cyclopolyene, arene, alkyl and carbonyl ligands.
Starting compound
Allyl complexes
Reagent
Reaction product
Ref.
Starting compound
Reagent
Reaction product
Ref.
Cyclopentadienyl complexes
(MeCp) U(THF) Me SiN
or PhN
AnCl
4
C
3
H
5
MgCl, Et
2
O
An(C
3
H
5
)
4
20,
3
3
3
(MeCp)
(R = Me
3
L UI
3
U = NR
20
96
4
4
3
3
Si, Ph)
U(C
Cyclopentadienyl complexes
Cp AnCl NaC10
3
H
5
)
4
HOR, Et
2
O
[U(C
3
H
5
)
2
(OR)
]
2 2
20
L
3
UH,
I
2
5 4
H
But,
(
L = Cp*, C
SiMe
AnCl
An = Th,U,Np)
Cp U, Cp
UBun
UBui
C
5
H
4
3
)
3
H
8
, THF
Cp
3
3
An(THF)
AnX
24,
Cp
3
RMgX in THF
or RLi in Et
Cp
3
AnR
20
or Na/Hg, THF
140
(
2
O
0
MX
M = Th, U, Np;
X = Cl, Br, I)
MeC
UBut
4
M Cp, DME
0
Cp
20,
44,
n
t
UBun,
UCH
UBn, Cp
4
3
Bu Cl, Bu Cl,
BnCl
Cp
3
Cp
3
Cp
3
147
(
(M = Na, K, Tl)
or Cp
3
2 2
CMe Cl,
141
3
UCl
t
(
5
H
4
)
3
C
2
H
4
or
(MeC
5
H
4
)
3
U(Bu )L
, CO)
142
or CpUBn
3
CO in PhMe
(L = C
2
H
4
Ã
Ã
.
Cp ThX
2
2
CpRu(CO)
2
Na
Cp (X)Th
2
24
20
20
20
Cp
3
UCl
UX
LiL (L = PPh
2
,
Cp
3
UL
U .
143 ±
145
(
X = Cl, Br)
Ru(Cp)(CO)
2
NEt
2 3
, SiPh )
Ã
Ã
Cp AnCl
2
2
LiR, Et
2
O
Cp AnR
2
2
Cp
3
2,6-Me
2
C
6
H
3
NC Cp
3
20,
145,
146
(
R = Alk)
(Me Si)
UX(THF)
[Cp BkCl]
2
.
(
X = NEt
PPh , SiPh
U(NEt
U=C(H)PPh
2
,
[Z -C(X)=N
Me
U(SnPh
UC:CPh
.
(
Me
3
Si)
2
C
5
H
3
UX
2
Na/Hg, THF
3
2 5 3
C H
2
3
)
C
6
H
3
2
-2,6]
Cp
3
3
2
)
HSnPh
3
Cp
3
3
3
)
24
24
BkCl
3
Cp
2
Be
2
2
Cp
2
Me HC:CPh
Cp

State-of-the-art coordination chemistry of radioactive elements
873
Table 4 (continued).
Starting compound
Reagent
Reaction product
Ref.
24
Starting compound
Reagent
Reaction product
[K(solv)][An(COT)
Ref.
Arene complexes
Cyclooctatetraene complexes
AnX (COT),
.
UCl
4
C
6
Me
6
,
[U
(m
3
(m
3
-Cl)
2
(m
2
-Cl)
.
3
3
K
2
2
]
152,
153
2
AlCl , Al
3
1
,Z -AlCl
4
)
3
(An = U, Np,
Pu, Am)
solvent
(solv)
6
(
Z -C
6
Me
6
)
3
](AlCl
4
)
Al, AlCl
3
, PhH
, C Me
(PhH)U(AlCl
[(C Me Cl
AlCl
]7
4
)
3
98
98
AnCl
4
COT, NaH
(COT)AnCl
2
(THF)
2
24
]+
7
.
(An = U, Th)
Zn, AlCl
3
6
6
6
6
)
2
U
2
[
4
U(BH
(PyH)
(COT)ThCl
4
)
4
COT
(COT)U(BH
Pu(COT)
4
)
2
24
20
Alkyl complexes
UCl
2
PuCl
6
K
2
(COT), THF
2
4
LiR, L
Li
2
UR
6
L
8
20
2
(THF)
2
Cp*MgCl(THF), (COT)ThCp*Cl(THF) 154
PhMe
(
L = THF, Et
2
O)
.
ThCl
4
LiMe, TMEDA, [Li(TMEDA)]
3
148
UI
3
(THF)
4
1) KCp*, THF
2) K (COT)
Cp*U(COT)(THF)
155
.
TMEDA a
Et
Cycloheptatriene complexes
UCl
UX
X = NEt
Cyclooctatetraene complexes
2
O
ThMe
7
2
Carbonyl complexes
U (vapour)
�
4
C
7
H
8
, THF
[U(Z-C
7
H
7
)
2
]
96
CO, Ar (4 K)
U(CO)
[(Me Si)
Cp M(CO)R
x
156
K(C
7
H
9
)
K[X
3
7
U .
7
149
[(Me
Cp MR
(M = U, Th, Np)
3
Si)
2
C
5
H
3
]U
CO
CO
3
2
C
5
H
3
]U(CO) 20
4
(
2
, BH
4
)
(m-Z :Z -C
7
H
7
)UX
5
]
3
3
44,
157
UCl
4
K
2
(COT)
U(COT)
2
150,
1
51
a
In this complex, six of seven CH
3
groups are involved in coordination to the Li(TMEDA)+ cations, two groups being coordinated to each of the cations;
TMEDA is tetramethylenediamine.
mixed ligands were prepared by treatment of An(COT)(BH
4
) with
thiol.1 Mono(cyclooctatetraene) amide uranium complexes
K[U(COT)(NEt ] and U(COT)(NEt (THF) were synthesised
Trimeric thorium complex 29 provides a rare example of
hydride complexes of early actinides, which are stabilised only
by the aryloxide ligands.90
37
2
)
2
2 2
)
from tetrakis(diethylamine)uranium and bis(cyclooctatetra-
ene)uranium, respectively. Oxidation of these complexes afforded
a series of uranium(V) derivatives.1
As can be seen from Table 4, actinide p-complexes containing
the cyclopolyene or arene ligands (see also Ref. 139) are more
abundant than actinide complexes with other ligands.
H , PhP, 1.5 atm, 7 days
2
Th(OAr)
2
(CH
2
SiMe
3 2
)
7
SiMe
4
38
ArO OAr
Th
H
H
H
H
OAr
OAr
ArO
Th
Th
H
H
VI. Hydride and hydroborate complexes of
actinides
ArO
2
9
t
2
Ar = C
6
H
3
Bu -2,6
The first organoactinide hydrides were prepared by hydrogena-
20
Ã
tion of Cp AnR
2
2
.
The complex 29 exhibits moderate catalytic activity in hydro-
genation of hex-1-ene.158 Alkoxide tetrahydroborate complexes
159
of uranium(IV) were also described.
Ã
Ã
2
Cp AnR
2
2
+ H
2
2
Cp AnH + 2 RH
Both monomeric and oligomeric hydride complexes of acti-
nides are available. Generally, these complexes contain OAlk, 1,2-
bis(dimethylphosphino)ethane (dmpe) or cyclopentadienyl as
additional ligands. Thus uranium and thorium tetrahydroborates
are polymeric compounds, whereas neptunium and plutonium
tetrahydroborates are monomeric. Methyltrihydroborate deriva-
Organoactinide hydrides are formed from the Ar AnR com-
n
plexes through metathesis of s-bonds.
20
d7
d+
H
H
Ar
n
AnR + H
2
n
Ar AnH + RH
Ar
n
An
R
d7
d+
tives An(MeBH
3 4
) always occur as monomers.
The structure of complex 30 was established.20 The geometric
parameters [the H7Th7Th and Th7H7Th angles are 58(1) 8
and 122(4) 8, respectively; the distance between the thorium atoms
is 4.007(8) A] indicate that the metal ± metal interaction in this
complex is weak.
0
8C
AnF + 2 Al(BH
4
4
)
3
4 4 2 4
An(BH ) + 2 AlF (BH )
ꢀ
The volatility of the complexes increases and their stability
decreases on going from thorium to plutonium.17
Thorium, neptunium, plutonium and protactinium hydro-
borates and uranium tris(tetrahydroborate) possess similar prop-
erties. However, Th, Np, Pu and Pa hydroborates have a number
H
H
of characteristic structural features.44 The UH(BH
(DME)
P(Py)]
4 3
)
Th
Th
complex contains the U7H bond. The U(BH [Ph
4
)
3
2
2
H
44
H
complex was also described in the cited study.
3
0

8
74
B I Kharisov, M A Mendez-Rojas
2
‡
The unusual electron-deficient cyclopentadienyl complexes
PPh U(BH and (C BH U(BH were
pyridine in the presence of UO2 gave rise to a hexaazamacrocy-
clic complex.17 When irradiated with neutrons, the
(C
5
H
4
2
)
2
4
)
2
5
H
4
3
)
2
4 2
)
160
described.
Other cyclopentadienyl and related hydroborate complexes,
2
phthalocyanine complex ThPc (Pc is phthalocyanine) entered
into the nuclear reaction to give the corresponding protactini-
17
um(IV) complex.
161
for example, [Na(THF)
ised.161, 162
6
][Cp*U(BH
4
)
3
]
2
,
were also synthes-
232ThPc
(n,g)233ThPc
233PaPc
2
2
2
Selected examples of hydride and hydroborate complexes of
actinides are listed in Table 5.
The phthalocyanine complexes AnPc
in a number of publications.170 ± 173
2
were described in detail
Complexes with other polydentate ligands, for example, with
chelating agents, can be used for efficient binding of actinide ions.
These complexes are soluble both in water and organic solvents.
Table 5. Selected hydride and hydroborate complexes of actinides.
1
7
Starting
compound
Reagent
Reaction product
Ref.
The higher the dentation of the ligand the more stable the
complex. In the An4+(EDTA) complexes (EDTA is ethylenedia-
minetetraacetic acid), the ligand is hexadentate and adopts a twist
conformation.17 Binding of plutonium and other radionuclides
can be carried out with the use of cyclic and linear catechol-
amines.1
UH
3
B
2
H
6
, THF
U(BH
4
4
)
3
3
(THF)
(THF)
3
2
44
44
U(BH
4
)
4
thermal decom- U(BH
position in
)
74
solution
Actinide complexes with crown ethers are generally prepared
from actinide salts. Complexes only with tri- and tetravalent
THF
Et
Li
U(BH
4
)
4
44
44
.
2
O
[U(BH
4
)
4
(Et
2
O)]
?
actinide ions are known {for example, [UCl
[UO Cl (OH)H
atoms of the ether and the water molecules of coordination were
3 2
(18-C-6)]
.
2
3
2
O]}. The hydrogen bonds between the oxygen
ThX
4
2
C
2
B
9
H
11
[Li(THF)
4
]
2
163
5
(
X = Cl, Br)
Th(Z -C
CpMgBr(THF) CpThBr
Th (m -H)
(OAr)
[UIV(Z -C
Li
Br
[Li(TMEDA)] .
2
B
9
H
11
)
2
X
2
2‡
17
found in the UO2 complexes. The IR spectra and the isotope
effects for uranium complexes with crown ethers and the crystal
structures of some of these compounds were published in the
literature.1
ThBr
4
(THF)
4
3
(THF)
3
164
90
.
.
Th(OAr)
2
H
2
3
3
2
2
(m -H)
4
75
(CH
2
SiMe
3
)
2
6
5
.
Actinide complexes with crown ethers can be prepared also
UBr
4
(MeCN)
2
Li
MeCN
Li
2
C
2
B
9
H
H
11
11
,
,
2
2
B
9
H
11
)
2
165
165
from organometallic compounds. Thus Cp
8-C-6 in the presence of a sodium amalgam in THF to yield
Cp UCl)[Na(18-C-6)] (see Ref. 24 and references cited therein).
3
UCl reacted with
2
]
1
UI
3
(THF)
4
2
C
2
B
9
(
3
TMEDA
dmpe
[U(C
2
B
9
H
11)I
2
(THF)
2
]
Ã
Ã
Cp UH
2
2
Cp U(H)Cl
2
20
VIII. Actinide complexes with nitrogen-containing
ligands
(Me
3
XC
5
H
4
)
3
UCl KHBEt
3
(Me
3
XC
5
H
4
)
3
UH
166
(X = C, Si)
Most of N-donor bases possess low affinity for actinides and act
predominantly as proton acceptors. The An7N bonds with
mono- and even bidentate N-donor ligands are rather weak.
Ã
Ã
Cp UH
3
Ph
Ph
3
3
3
PBH
3
Cp UBH
3
4
96
96
But)
SiMe
Me
Cl(THF)] or
U(Z-C R)
R = H, Bu,
SiMe
Cp MR
M = U, Th)
UH
PBH
PBH
(C
H
H
But)
UBH
UBH
UH
17
(
C
5
5
H
4
4
3
3
3
5
5
4
4
3
4
2 2
The complex UO (hfa) exhibiting high acidity forms a 1 : 1
(C
H
3
)
3
UH Ph
(C
SiMe
3
)
3
4
96
complex only with ammonia. Like actinide alkoxides, actinide
amides occur generally in the associated form. For example, these
compounds react with chelating N,N '-dimethylethylenediamine
.
] .
.
[
U(Z-C
5
5
)
2
[K(THF)
[ReH (PPh
2
K[Cl(Z-C
3 2
Re(PPh )
5
Me
] or
R)
5
)
2
6
167
6
3
)
2
]
.
[
5
H
4
3
Cl]
[U(Z-C
Re(PPh ) ]
3 2
5
H
4
3
UH
6
to give the linear trimeric [U(dmed)
tetrameric [U(dmed)
complex.17, 176 Dialkylamide and related
complexes, such as U[N(SiMe , [U(NEt ]BF , U(NPh
2 MeCONEt , were
2 3
] complex and the square
(
2 4
]
3
)
3
)
2
]
3
2
)
3
4
2 4
) ,
.
.
.
2
2
H
2
Cp
2
M(H)(m-H)
2
44
UO
described in the literature.
The structure of the U[N(SiMe
B(C ]}] complex was established by X-ray and neutron
2
[N(SiMe
3
)
2
]
2
(OPPh
3
9
)
2
and UO
2
CrO
4
2
7, 177 ± 182
(
M(H)Cp
2
5
.
5
UIIIBr .
3 2 3 2
) {N(SiMe )[SiMe 7
[
(Z -C
2
B
9
H
11
)
2
electrochemical [(Z -C
2
B
9
H
11
)
2
168
IVBr
] .
.
CH
2
6 5 3
F )
U
2
reduction and
x
(THF)] 2 [Li(THF) ]
diffraction analysis. It was demonstrated that the electron defi-
ciency on the uranium atom is effectively compensated by the
formation of multicentre bonds between the U atom and the
2
[Li(THF)
4
]
reduction
(x = 2 ± 4)
with Na/Hg
2
SiCH groups of the amine ligands. The X-ray diffraction data are
3
unambiguously indicative of m -coordination of the BH
4
groups.1 The structure of the unusual uranium(III) complex
83
VII. Actinide complexes with macrocyclic ligands
0
with a tripodal aromatic amine, viz., tris[(2,2 -bipyridin-6-
1
84
Data on several actinide complexes with crown ethers and other
macrocyclic ligands were published in the literature. Thus treat-
ment of uranium and thorium tetrakis(diethylamides)
yl)]amine, was established by X-ray diffraction analysis.
Protolysis of the U7N bond in amide complexes of uranium
affords cationic complexes. This procedure was used for the
[
An(NEt
2
)
non-planar sandwich complexes An(TPP)
4
] with free porphyrin (TPP) afforded the diporphyrin
Ultrafast electronic
synthesis
[U(Z-Cp)
of
compounds
containing
(THF)
the
cations
.
17
+
+
2
.
3
(THF)] , [U(Z-Cp*)(NEt
2
)
2
2
5 5 2
] , [(U-Z-C R )
+
+
185
deactivation and the vibrational dynamics for the excited states of
the uranium(IV) porphyrin sandwich complexes were exam-
ined.1
(NEt
[U(NEt
U complexes with the silylated N(CH
2
)(THF)] , [U(Z-C
5
R
5
)(Z-COT)(THF)
2
]
(R = H, Me),
, etc. The resulting Th and
CH NSiMe ligand con-
+
2+
177
2 3 2 2 3
) ] , [U(NEt ) (THF) ]
69
2
2
3 3
)
General procedures for the preparation of actinide complexes
with macrocyclic Schiff's bases involve direct binding of the metal
ion with the corresponding ligand and cyclisation in the presence
of the metal ion. Thus phthalodinitrile reacted with anhydrous
uranyl dichloride in DMF to give a `superphthalocyanine' uranyl
complex. Condensation of ethylenediamine with 2,6-dicarbonyl-
tain bonds between the metal atoms and the chlorine, carbon,
hydrogen or oxygen atoms.1 Chloro, pentamethylcyclopenta-
dienyl and tetrahydroborate complexes of uranium containing the
86
N(CH
diffraction method.
2
CH
2
NSiMe
3
)
3
ligand were characterised by the X-ray
The reactions of actinide amides were
186
surveyed in a recent review.1
87

State-of-the-art coordination chemistry of radioactive elements
Only several imide complexes of actinides are known:
875
The complex 34 was obtained as red paramagnetic crystals
The
N(CH CH NHSiMe ) ligand ensures the optimum spatial envi-
ronment for stabilisation of this complex. Since thorium(IV)
compounds are diamagnetic, the diazabutadiene ligand in the
paramagnetic complex 34 is subjected to one-electron reduction,
i.e., this ligand is present as the [Bu DAB] radical anion.
The complex formation of neptunium(VI) with 3,3 -bis(diazir-
idine) derivatives 199 and of uranium(VI) with 8-hydroxyquinoline
V
VI
Me
3
SiN=U [N(SiMe
3
)
2
]
3
,
Me
3
SiN=U F[N(SiMe
Me)]Cp
U=NR type (R = Ph or SiMe
both lone electron pairs of nitrogen are involved in binding with
3
)
2
]
3
,
Cp
2
.
(monoclinic, space
the
group
is
P2
1
/n).
t
188, 189
.
U(NC
6
H
2
Bu -2,4,6) and U[N(CHMeCH=PPh
2
3
.
2
2
3 3
3
In complexes of the (C
5
H
4
Me)
3
3
),
uranium.2
4, 190
Of the simplest nitrogen-containing ligands, the
azide anion gives very stable complexes with uranium
t
2
�
diss = 56107 ). The stabilities of the latter complexes are
3
0
(K
17
comparable with those of fluoride complexes. The binuclear
U7Mo) heterocomplexes with N
were prepared.191 IR spectro-
scopic and quasirelativistic theoretical studies of the coordination
and activation of N with the uranium and thorium atoms were
carried out virtually at the same time.
200
(
2
and its 5-halogen derivatives was studied. In the latter case, the
UO
derivative) were obtained.
2 2 2
L and UO L complexes (where L is a 8-hydroxyquinoline
200
2
192
Considerable recent attention has been given to uranium
complexes with Schiff's bases (see, for example, the review 201).
Uranium(VI) complexes with Schiff's bases are used as organic
oxidants (the catalytic modifications of these reactions were also
Ã
The mononuclear UCp (NHR)
2
complexes (R = 2,6-
2 6 3
Me C H , Et or Bu) were synthesised, their structures were
2
established and these complexes were demonstrated to catalyse
hydroamination of terminal alkynes with ammonia.1 The data
on complex formation of uranium(VI) with neutral N-donors in
DMSO were reported. 1
93
202
developed). Polystyrene-supported chelating resins incorporat-
2
03, 204
ing U(VI) complexes with Schiff's bases are available.
205
94
203
Salicylaldehyde
and triethylenetetramine, 3-formylsalicylic
acid and o-hydroxybenzylamine 204 or salicylaldehyde and
An analogue of the uranyl ion was found in the crystal
7
‡
206
structure of the red complex PPh {UOCl
4
(
3
accompanied by elimination of Me
4
[NP(C
6
H
4
Me-3)
3
]}
1-amino-2-hydroxynaphthalene-4-sulfonic acid
were used as
31).1 The air-stable complex 31 was prepared from compound
95
precursors of Schiff's bases. Uranium(VI) complexes with Schiff's
bases exhibit photochromic properties. The kinetics and the
mechanisms of photochromic conversions were examined.
Examples of actinide complexes with nitrogen-containing
ligands are given in Table 6.
7
2 by the replacement of the chloride ligand in the [UOCl
SiCl.
5
] anion
2
07
3
CH
2
Cl
2
‡
5 3 6 4 3
PPh [UOCl Si[NP(C H Me-3) ]
]7 + Me
4
7Me
3
SiCl
32
‡
4 6 4 3
PPh {UOCl [NP(C H Me-3)
]}7
4
Table 6. Selected actinide complexes with nitrogen-containing ligands.
31
Starting compound
Reagents
Reaction products
Ref.
208
According to the data of X-ray diffraction analysis, the
7
{
UOCl
4
[NP(C
6
H
4
Me-3)
3
]} ion contains the linear O=U=N
.
UO
2
Cl
2
KN(SiMe
THF
3
)
2
,
UO
(THF)
Th(NPh
or K[Th(NMePh
U[N(SiMe
2 3 2 2
[N(SiMe ) ]
195
group coordinated by four chlorine atoms. The U7O distance
2
ꢀ
1.76 A) is typical of the uranyl ion (see Ref. 195 and references
(
ThBr
4
(THF)
4
KNR
2
2
)
4
(THF)
44,
ꢀ
cited therein). The U7N distance (1.90 A) indicates that the bond
order is no less than 2. The U7N7P group is nearly linear
5
)]
110
(171.9 8), which suggests that the p electrons of the nitrogen atom
UCl
3
(THF)
3
NaN(SiMe
THF
3
)
2
,
3
)
]
2 3
112
are completely involved in bonding with uranium. The orders of
the bonds between the uranium atom and each of the oxygen
atoms in the uranyl ion can be equal to 3 due to the fact that the
uranium atom bears simultaneously f and d valence orbitals.1
Other anionic actinide complexes can be prepared immedi-
.
U(NPh
2
)
4
L
U(NPh
U(NPh
2
2
)
)
4
4
L
180
(
L = Py, Et
THF, (EtO)
Ph NH
2
O,
95, 196
3
PO)
(
NSiMe
CH SiMe
UCl
HMe
2
)
2
U .
NSiMe
2
44
5 6
ately from salts. For example, UF and UF react with nitrogen
2
2
3
bases to give molecular or ionic compounds, such as
+
]7, UF
12(bipy).197
[
(bipy)
Thermolysis of the thorium derivative Th(OSO
[N(SiMe in the presence of 1 equiv. of pentamethylcyclopen-
2
H] [UF
6
4
(2-FC
5
H
4
N) and U
2
F
4
LiNEt
2
U(NEt
2
)
4
44
2
CF
3
).
2
Si
NSiMe
Th
3
.
3
)
2
]
3
.
HNMePh
Th[N(SiMe
(NMePh)
3
)
2
]
2
110
111
tadiene afforded binuclear complex 33.
(Me
3
Si)
2
N
N(SiMe
3
)
2
2
OTf
1
10 8C, 8 days
N[ThN .
1) CF
2) CpH
Cp[(Me
(m -OSO
Th[N(SiMe)
(SiHMe CH)]Cp
208
3
Si)
2
3
SO
3
H
3 2
Si)
N]Th .
Th N(SiMe
N(SiMe
3
)
2
+ 2 Cp*H
(Me
SiMe
(SiHMe
3 2
(Me Si) N
PhMe
) .
.
(
3
2
2 3 3
CF )
3 2
)
.
CF
O
3
2
CH)]
3
O
CF3
O
2
S
S
Cp
3
U=C(H)PPh
2
Me HNPh
RN
3
R = Me Si,
2
Cp
3
UNPh
Me)
2
24
O
O
(
C
5
H
4
Me) U(THF)
3
3
(C
5
H
4
3
U=NR
190
O
Th
Th
O
(
O
Me
3
Si
N
3 2
N(SiMe )
CH
2
Ph)
S
NEt
U
2
Si
Me
Me
O
CF
3
Cp
2
NR
Cp U(NEt )
2
2 2
RNC
44
33
NEt
2
The actinide complex with 1,4-di-tert-butyl-1,4-diazabuta-
diene (DAB) 34 was prepared for the first time from the complex
(tren) as a ligand.1
THF
98
containing N(CH
2
CH
2
NHSiMe
3
)
3
t
2
[
(tren)ThCl]
2
+ 2 Li[Bu (DAB)
2
]
7
80 8C
IX. Complexes with phosphorus-containing ligands
t
2
t
2
2
(tren)Th[Bu (DAB)] + 2 {Li[Bu (DAB)]}Cl
A large number of actinide complexes, which bear oxygen-
containing phosphorus ligands and in which the metal atom is
34

8
76
B I Kharisov, M A Mendez-Rojas
coordinated by the oxygen atom, are available.17 Examples of
phosphine complexes containing the An7P bond are few in
number.2 Thus thorium(IV) and uranium(IV) tetrahalides react
Examples of actinide complexes with phosphorus-containing
ligands are given in Table 7.
09
with trimethylphosphine to give the 1 : 2 complexes MCl
7, 210
4
(PMe
The U[Me PCH CH PMe ] complex con-
3 2
)
X. Sulfur-containing actinide complexes
(
M = U or Th).1
2 2 2 2 4
taining an eight-coordinate uranium atom, which is isostructural
to the thorium analogue, was described. 2 Uranium complexes
with phosphorus donor ligands, procedures for their synthesis,
structures and properties were considered in the study. 2
Being hard acids, actinides usually do not form stable complexes
with S-donor ligands, which are soft bases. Only a few examples of
complexes with sulfur-containing ligands are available in the
11
12
literature, viz., UCl
An(S CNEt (An = Th, U, Np or Pu), (NEt
(NMe )[UO
[U(SPh)
only known uranium(V) complex containing the metal ± sulfur
4
(dmte)
2
(dmte is 1,2-dimethylthioethane),
)[Np(S CNEt ],
[U(SBun) ]27 and
[Na(18-C-6) (THF)][U(COT)(C ] is the
Ligands of the phosphacyclopentadienyl type serve as bridges,
for example, in the dimeric uranium(III) complex 27.24, 134, 213
The reactions of lithium salts of the potentially tridentate
2
2
)
4
4
2
2 4
)
17
n
4
2
(S
2
CNEt
2
)
3
],
U(SBu )
4
,
6
2
7 224
.
6
]
;
4 4 4 2
H S )
2�
i
diphosphinoamide ligands N(CH
2
CH
2
PR
2
)
(R = Et or Pr )
2
25
with uranium or thorium tetrachlorides afforded diphosphinoa-
mide complexes of actinides. Ligands of this type are suitable for
the preparation of various complexes of uranium(IV) (for exam-
bond.
4 2 2 2
The reaction of UCl with Li (SCH CH S) in dime-
thoxyethane afforded 2 the first homoleptic dithiolate complex
26
of an f element (36; the space group is P2
1
/n).
2 2 2 2 2 2 2
ple, {UCl [N(CH CH PEt ) ] } ), uranium(V) and thorium(IV).
DME
Depending on the reaction conditions, these ligands can be
mono-, bi- and tridentate. The character of the coordination
compounds can be radically changed by varying the substituents
at the neutral phosphine centre.2
] . DME
2 2 4
CH S)
UCl
4
+ 4 Li
2
(SCH
2
CH
2
S)
[Li(DME)]
4
[U(SCH
3
6
14
The nature of the U7S bond in the complex 36 was estimated
by the semiempirical Huckel method. It was found that the 6d, 7s
Thorium and uranium complexes with diphosphazane diox-
ides were synthesised.215 The crystal structure of the
UO (NO ) [Ph P(O)N(Ph)P(O)Ph ] complex was established. It
2 3 2 2 2
È
and 7p orbitals of uranium are responsible for interactions with
sulfur-containing ligands. The involvement of 5f orbitals is insig-
nificant, and hence, the p interaction between uranium and sulfur
is weak.2 The authors also gave a brief review of the state of the
art in the chemistry of actinide ions with sulfur-containing
was demonstrated that the metal atom is coordinated by diphos-
phazane dioxide in a bidentate fashion. Some other organo-
phosphorus and related compounds of uranium were described
in the studies.2
26
16 ± 219
226
ligands.
Actinide complexes containing simultaneously the phosphine
and cyclopentadienyl ligands are few in number. Only the
Derivatives of uranium(IV) tetrathiolate were prepared by
n
treatment of U(NEt
2
)
4
, U(BH
oxidation of metallic uranium with disulfides. It was found that
4
)
4
or U(SBu )
4
with thiols and by
227
Cp
2
ThX
2
(Me
2
PCH
2
CH
2
PMe
2
)
complexes (X = Cl, Me or
Bn) 1 and monomeric hydride complex of uranium(III) 35 were
79
i
4 2 2
the reactions of the U(SBu ) complex with acids, I and CS
prepared.2
20
proceeded at the U7S bond.
The neptunium(V) complex with DMSO with composition
227
Me
P
2
2
.
H
[(NpO
2
)
2
28
(DMSO)
7
(H
The structure contains the dimeric complex
(DMSO) (H O)
]+ cations, perchlorate anions, coordi-
2 2 4 2 2
O) ](ClO ) H O was structurally charac-
Ã
2
terised.2
[(NpO
PhMe, H
Cp UR
2
2
+ Me
2
PCH
2
CH
2
PMe
2
U
autoclave, 720 8C
2
)
2
7
2
2
P
Me
nated water molecules and water molecules of crystallisation. The
IR and electronic spectra are indicative of the non-equivalence of
the dioxo cations. Thus Np(1)O2 acts as a monodentate ligand,
‡
R = Me, CH
2
SiMe
3
.
35
whereas Np(2)O2 serves as the coordination centre.228
‡
The reactions of U(BH
ligands afforded the U(BH
phinoethane 2 or 2-(diphenylphosphino)pyridine ]. In these
compounds, dynamic transformations are observed within the
NMR time scale even at low temperature.
4
)
3
(THF)
x
with some diphosphine
4 2
Treatment of the U(COT)(BH ) complex with thiols or
sodium thiolates (RSH or RSNa, where R = Bu , Pr or Bu )
afforded first organouranium compounds containing the bridging
n
i
t
4
)
3
(L) complexes [L is dimethylphos-
2
21
222
disulfide {[U(COT)(m-S)
groups. The structures of these compounds differ from those of
2
]
2
2 2
} and thiolate {[U(COT)(m-SR) ] }
their alkoxide analogues, which contain only two bridging OR
groups.2
29
Table 7. Selected actinide complexes with phosphorus-containing ligands.
i
The reaction of U(NEt
2
)
rise to the first structurally characterised tetrathiolate complex of
4
with Pr SH and OP(NMe
2
)
3
gave
Substrate
AnCl
Reagent
Product
Ref.
i
229
uranium U(SPr )
t
4
[OP(NMe
t
2
)
3
]
2
.
(SBu )
The uranium sulfur cluster
230
was also described.
t
U
3
(m
3
-S)(m
3
-SBu )(m
2
-SBu )
3
6
4
MP(CH
2
CH
2
PMe
2
)
2
An[P(CH
2
CH
2
PMe
2
)
]
2 4
211,
214
Ã
The Cp U(dddt) complex (dddt is 5,6-dihydro-1,4-dithiin-2,3-
dithiolate) 231 and the homoleptic uranium(IV) complexes
M = Li, K
An = Th, U
2
i
2�
.
i
0:5
ThCl
4
[N(CH
‡
2
CH
2
PPr ]
ThCl
2
[NCH
2
CH
2
PPr
]
2
211,
214
t
2
(
THF)
3
Na(m-SR)
3
U(m-SR)
3
Na(THF)
3
(R = Bu or Ph) were syn-
Li
232
2
thesised.
Recently, the first heteroleptic uranium(V) complex 38 was
2�
.
.
UCl
4
[N(CH
‡
2
CH
2
PEt2]
{UCl
CH PEt2)
[UOCl
NP .
(C Me-3)
UO
2
[N(CH
2
211,
214
2
33
Li
2
]
2 2
}
2
4
prepared by oxidation of complex 37 with AgBPh in THF.
2
�
Si[NP .
[
UOCl
5
]
Me
3
4
189
(
COT)UX
2
(THF)
n 2
+ Na (dddt)
�
(see a)
3
]
(C
6
H
4
Me-3)
3
]
6
H
4
AgBPh
THF
4
[
(COT)UIV(dddt)
][Na(18-C-6)]
2 2
.
KOBut
(OBut)
.
UO
2
Cl
2
2
2
181
181
3
7
(Ph
3
PO)
2
(Ph
3
PO)
2
.
NaN(SiMe
3
)
2
UO
2
3 2 2
[N(SiMe ) ]
(
3 2
Ph PO)
U
S
S
Ã
Ã
) b
Cp UCl
2
2
HNPPh
3
Cp UCl
2
2
(HNPPh
3
223
S
S
S
S
a
P+ cation is air-stable and is soluble in
4
The red salt containing the Ph
Cl
and MeCN; b the first complex of the f element with the
phosphineimino ligand.
S
S
CH
2
2
38
4
X = BH , n = 0; X = I, n = 1.

State-of-the-art coordination chemistry of radioactive elements
877
Notwithstanding the fact that the available sulfur-containing
actinide complexes are few in number, these compounds are of
latter was used for the synthesis of the Tc(C
.(NNC N)(HNNC N) complex (C NS is pyridine-2-thi-
olate), which is a precursor of Tc-containing peptide reagents
5 4 2
H NS) .
5
H
4
5
H
4
5 4
H
230
99m
great interest in the coordination chemistry and can find use for
extraction of actinides.2
32
for medical investigations. The bifunctional hydrazine ligands
used in the study 2 are efficient and versatile linkers for labelling
antibodies and protein fragments. Other organic hydrazine com-
38
Examples of sulfur-containing uranium complexes are given
in Table 8.
plexes of 9 Tc were also prepared. The reactions of [TcOCl
with hydrazine hydrochloride (PhMe, 20 8C or CH Cl , 36 8C)
] 0.75 PhMe and
The exchange
with 2-hydrazinopyridine
9m
]
7
4
2
2
Table 8. Selected sulfur-containing uranium complexes.
.
gave
TcNCl
rise
(PPh
to
[TcCl
2
(C
Cl
8
H
5
N
4
)(PPh
respectively.
Cl
3 2
)
] . 0.25 CH
,
239
[
2
3
)
2
2
2
Starting
compound
Reagents
Product
Ref.
232
reaction of Tc(MeCN)(PPh
afforded Tc(III) complex 39.2
3
)
2
3
40
UCl
4
NaSR (R =
t
(THF)
3
Na(m-SR)
Na(THF)
3
3
U .
or U(BH
4
)
4
Bu , Ph), THF
(m-SR)
3
PPh
3
N
Cl
Cl
UI
4
DMSO
DIBSO
UI
UI
4
(DMSO)
n
(n = 6, 8) 104
(n = 6, 8)
Tc
4
(DIBSO)
n
N
N
PPh
3
Ã
Ã
2
Cp UCl
2
2
Na
2
(dddt)
Cp U(dddt)
230
3
9
i
U(SPri)
U(NEt
2
)
4
Pr SH,
4
[OP(NMe
2
)
3
]
2
233
Complexes with compositions mer-[Cl
(pic)(PMe Ph) Tc] (pic is 4-picoline) were prepared by the
reactions of [TcOCl
-picoline. The process was accompanied by the oxygen atom
3 3
(pic) Tc] and mer-
2 3
(Me N) PO
[
Cl
3
2
2
7
4
]
with a series of phosphine ligands in
4
migration. The resulting compounds were characterised by spec-
troscopic methods and X-ray diffraction analysis.2
Complexes of high oxidation state technetium containing the
XI. Technetium complexes
41
The chemistry of technetium becomes increasingly important,
particularly, due to the fact that the short-lived (T1/2 6.015 h, g
irradiator) nuclide 99mTc is used in diagnostic medicine. This
nuclide has been used over many years in bone scanning. Recently,
2+
[Tc:N] core are more stable than the corresponding complexes
3+
of technecyl [Tc=O]
technecyl derivatives.
and their properties resemble those of
99m
.
Tc has found use in the treatment of various diseases of the
The technetium(V) complex [TcN(L)(H
tetraazamacrocycle) was prepared by the reaction of
TcNCl (PPh ) with the tetraazamacrocycle. A complex with
2 3 2
2
O)] 2 H
2
O (L is the
heart, brain, kidney, liver and other organs as well as of tumour
tissues. Technetium complexes are also of interest in the radio-
pharmaceutical industry.2 Owing to the ideal energy of g
radiation (140 keV), lack of particulate radiation dose, the small
242
34
2+
the [Tc:N] core was synthesised using ancillary polydentate
phosphorus- and nitrogen-containing ligands. The reaction of
half-life T1/2 and the fact that 9 Tc is readily accessible, this
isotope is a radionuclide of choice for obtaining images in
diagnostic nuclear medicine.2
9m
[TcNBr
dral [TcNBr(bipy)
containing the tetrahedral tetrabromo technetate(II) cation.
Other chelate nitride complexes of technetium(V) with the
]
7
0
with 2,2 -bipyridyl in ethanol afforded the cis-octahe-
4
2
+
2
]
2
(TcBr
4
) complex with the [Tc:N]
core
35, 236
243
2+
1
. Complexes with nitrogen-containing ligands
N
reactions of TcNCl
2
S
2
ligand and the [Tc:N]
core were prepared by the
Complexes of Tc(III), Tc(II) and Tc(I) with pyridine ligands were
prepared.2 The authors were interested to prepare a coordina-
tively unsaturated low-valence electron-rich Tc metal centre
surrounded by very weak p-donor ligands.
2
(PPh
3
)
2
2 2 2 2
with (HSCR CH NRCH )
37
244
(R = Me or Et).
V
Since the chemical behaviour of the Mo O complexes is
similar to that of the TcVIN complexes, pertechnate complexes
can be synthesised according to the procedure developed for the
Tl+, Py, D
trans-[TcCl
2
(Py)
4
]+
preparation of analogous Mo O complexes. Thus chelate nitride
V
PPh
Tc
3
Cl
Tl+, Py
Cl
Cl
complexes of technetium(V) with ligands of the N
2
S
2
type and the
(m-O) [TcN.
(m-O) } and (AsPh
2 2 2
(m-O) } [edt = S(CH ) S], were prepared by the
+
trans-[TcCl (Py) (PPh )]
2
3
3
MeCN
2+
[
Tc:N]
.(S CNC
.{[TcN(edt)]
reactions of {[TcN(OH
cursors of the corresponding ligands in solutions of Na
The reaction of TcNCl (PPh with the piperidinium ferro-
cenyldithiocarboxylate gave rise to nitride complex 40. According
core,
(m-O)
viz.,
, (AsPh
[TcN(S
{[TcN(CN)]
2
CNEt
2
)]
2
2
,
tpy, DME, 20 8C
PPh
3
4
H
)]
)
4 2
4 2
) .
mer-TcCl(tpy)
2
8
2
2
2
2
tpy is terpyridine.
2
2
)
3
]
2
2 2 5
(m-O) (TcNCl ) with pre-
}2 or Cs
+
t
3
245
The TcCl
and [Tc(tpy)(Py)
2
(Py)
4
, TcCl
3
(PPh
3
)
2
(TMEDA), TcCl
]Cl compounds were characterised by electro-
3
[Bu (tpy)]
4 2 7
P O .
3
2
3 2
)
chemical and spectroscopic methods and by X-ray diffraction
analysis.2 According to the data of this investigation, p-back
bonding is observed in the Tc(II) and Tc(I) complexes, unlike the
Tc(III) complexes. In particular, the Tc7N bonds in pyridine
37
246
to the data of cyclic voltammetry,
two iron(II) atoms in the
complex 40 act as independent redox centres linked through the
[Tc:N] core. Chelate complexes 41 and 42 containing the same
ꢀ
247
complexes of Tc(II) are shortened by 0.04 ± 0.06 A and the
Tc7N(internal) bonds in terpyridine complexes of Tc(I) are
[Tc:N] core were also synthesised.
S
ꢀ
shortened by 0.09 A compared to those in the analogous Tc(III)
+
complexes.2 These effects are favourable for stabilisation of low
37
N
S7
H N
2
Cl
Cl
oxidation states of the metal atoms. The pyridine Tc(III) com-
1
Tc
Fe
2
+
plexes give Knight-shifted H NMR spectra. The visible regions
Ph3P
PPh3
of the spectra show transitions, which were empirically assigned to
ligand-to-metal charge transfer transitions; multiple reversible
electrochemical redox couples were found.237
Reduction of pertechnates (as well as perrhenates or permo-
lybdates) with 2-hydrazinopyridine hydrochloride in methanol
N
S
S
Tc
S
S
Fe
Fe
1
2
afforded complexes containing the M(Z -NNC
5
H
4
NH
x
)(Z -
4
0
38
y 5 4
C H
N) core (M = Tc, Re or Mo).2 In particular, the
HNNH
5 4 5 4
TcCl (NNC H NH)(HNNC H N) complex was prepared. The
3

8
78
B I Kharisov, M A Mendez-Rojas
N
and Tc7P distances are 2.318(6) A and 2.902(7) A, respectively;
the S7Tc7S angle is 84.49(4) 8].
ꢀ
ꢀ
Ph
Ph
3
P
P
Cl
Tc
+ 2 Na
2
(SPPh
2
NPPh
2
S)
Refluxing of the salt (NBu
with dihydrooxazoles and dihydrothiazoles, for example, with
-(2-hydroxyphenyl)-4,5-dihydrooxazole, 2-(2-hydroxy-3-meth-
ylphenyl)-4,5-dihydrooxazole or 2-(2-hydroxyphenyl)-4,5-dihy-
4 4
)(TcOCl ) in alcoholic solution
3
PPh
3
N
Ph
N
2
P
P
S
S
S
PPh
2
2
2
Tc
N
Ph
2
S
PPh
drothiazole, yielded the six-coordinate complexes TcOClL
the corresponding (hydroxyphenyl)dihydrooxazole
2
(L is
or
41
2 2
NaN(SPPh )
thiazole).256
-
TcNCl
2
(PPhMe
2
)
2
2 2 2
TcN(Cl)(PPhMe )[N(SPPh ) ]
The reaction of ammonium pertechnate with 3,5-di-tert-
butylpyrocatechol (DBCat) in methanol afforded a mixture of
the Tc (DBCat) and Tc (DBCat) (DBAP) complexes (DBAP
3 2
is the amidophenoxide ligand). The amidophenoxide ligand is
formed through condensation of ammonia (from ammonium
pertechnate) with pyrocatechol to give the Schiff's base. Accord-
ing to the data of EPR spectroscopy and X-ray diffraction
analysis, technetium in the complex exists in oxidation state +6,
which is very untypical. The DBCat ligand serves both as a
reducing and chelating agent.
4
2
VI
VI
The possibility of radiopharmaceutical application of nitride
technetium complexes with nitrogen-substituted amino acids, viz.,
derivatives of 2,5-dimethyldithiocarbamic acid, was reported.
Complexes with composition TcN(L )(PPh
dtc (n = 1), Z-Ala-dtc (n = 2), Z-Phe-dtc (n = 3), Z-Val-dtc
n = 4) or Z-Leu-dtc (n = 5), were synthesised. All these com-
plexes were characterised by spectral methods and X-ray diffrac-
tion analysis.
257
248
n
n
3
), where L = Z-Gly-
(
Binuclear complexes of Tc(VII) 43 and Tc(VI) 44 were syn-
thesised by reduction of complexes 45 and 46, respectively, with
sodium.2
3. Complexes with nitrogen- and sulfur-containing ligands
The HTcO(cysteine)
49
2
complex (47) and its barium salt
58
were synthesised.2 These compounds are
Ba[TcO(cysteine)
of importance in biology and medicine. The properties of these
2 2
]
Na
Tc(NC
6
H
3
Me
2
-2,6)
3
I
Tc
2
(NC
6
H
3
Me
2
-2,6)
4
(m-NC
6
H
3
Me
2
-2,6)
2
4
5
43
complexes were studied.
Na
NH OAc,
4
i
i
.
Tc(NC
6
H
3
Pr -2,6)
3
I
Tc(NC
6
H
3
Pr -2,6)
6
2
NH HCl
2
2
pH 7.4
46
44
Bu
4
NTcOCl
4
+ HSCH
2 2
CHCO H
The crystal structure of the complex 43 consists of tetrahedra
linked via shared edges, whereas the complex 44 has an `ethylene-
H2
N
H2
N
O
O
249
Tc
O
OH
like' structure. The reaction of the pertechnate ion with the salt
.
S
0
S
of 3,6-bis(2 -pyridyl-1,2,4,5-tetrazine) (bptz 2 HCl) in methanol
or ethanol afforded binuclear complexes of the general formula
O
4
7
(
m-bptz)(TcO
3
X)
2
(X = Cl, OMe or OEt) containing Tc(VII),
0
Tc(V) and the bridging bptz ligand. 4-Phenyl-3,6-bis(2 -pyridyl)-
pyridazine (pppz) was used as a ligand for the preparation of
The complex 47 can be synthesised starting from ammonium
pertechnate and cysteine. All previous attempts to prepare tech-
netium complexes with cysteine afforded products contaminated
mononuclear complexes from pertechnate and TcOCl
4
in an
aqueous-ethanolic solution of HCl.2 The binuclear polypyridyl
oxo-bridged technetium(III) complex {(tpy)[Me (bipy)]Tc7
O7Tc(tpy)[Me (bipy)]}(OTf) was prepared by the reaction of
TcCl
(tpy) with thallium triflate in the presence of water.2
The synthesis of diazene technetium complexes was
described.252
Thus the TcCl(NNR) (PPh complex
R = C Cl-4), which was prepared from TcOCl4 and mono-
substituted hydrazine RNHNH in methanol, reacted with the
bidentate S CNR ligand and maltol to give Tc(NNR)L (PPh
and TcCl(NNR)L(PPh
The template synthesis from tetrabutylammonium pertech-
nate (NBu )(TcOCl ) or (NH (TcXO) (X = Cl or Br) followed
50
258
259 ± 263
by polymeric compounds.
It was also reported
that
2
chelation of technetium with polyfunctional ligands was accom-
panied by the formation of polymeric by-products. It is believed
that an excess of the ligand causes decomposition of the initially
formed chelate. The use of S-protective groups (for example,
benzyl, acetylaminomethyl or benzoylaminomethyl) prevents the
formation of undesirable polymeric products.
The technetium (99mTc) analogue of oxorhenium bis-cystei-
nate possesses valuable biological properties. In particular, it is
2
4
51
3
2
3 2
)
�
258
(
6
H
4
2
2
2
2
3
)
2
52
264
3
) (L = S
2
CNR
2
) in high yields.
accumulated in kidneys, which is useful in diagnostics of the
58
morphological status of this organ.2
4
4
4
)
2
Potential radiopharmaceuticals for diagnostics of the renal
function were synthesised with the use of chelating carboxyl-
containing ligands bearing N- and S-centres . The carboxyl groups
favour the renal uptake of these compounds.2 The TcO(ECH
complex was prepared based on the ammonium salt NH (TcOX
4
(X = Hal) and (2R,7R)-2,7-dicarboxy-3,6-diaza-1,8-octanedi-
thiol (ECH ). In the isostructural rhenium(V) complex, one of
the carboxyl groups in the trans position with respect to the oxo
ligand is coordinated in an unexpected fashion.2
The choice of other ligands, viz., Schiff's bases, was governed
by their tendency to be coordinated to technetium in various
unusual oxidation states. The chemistry of technetium(I) com-
plexes is poorly known. Only a few compounds were identified
by reduction by divalent tin afforded seven-coordinate Tc(III)
complexes, for example, such as the monocapped adduct of boric
acid with technetium(III) trisdioximate or TcX(dioxime) BR
64
99
3
3
4
)
)
(X = Cl or Br; dioxime = dimethylglyoxime or cyclohexanone
dioxime; R = Me or Bu).
253
A technetium(III) complex containing acetonitrile, viz.,
TcCl (MeCN)(PR (R = Ph or C Me-3), was prepared by
reduction of TcCl (PPh with zinc in acetonitrile in the presence
of PPh . This complex is a convenient intermediate in the synthesis
3
3
3
)
2
6
H
4
65
4
3 2
)
3
of other Tc(III) compounds. Its reactions with bipy, 1,10-phenan-
throline (phen) and tpy afforded dicationic Tc(III) complexes, viz.,
2+
2+
2+
[
salts with BPh4 or PF .
Tc(bipy)
3
]
, [Tc(phen)
3
]
254
and [Tc(tpy)
3
]
, respectively, as
�
�
3 2 3
and characterised. The reaction of (PPh ) (CO) Cl with the
6
lithium salt of Schiff's base, viz., N-ortho-hydroxybenzylidene-2-
thiazolylimine, in boiling THF gave rise to the Tc(I) complex with
2
Reduction of [Tc(OH)O(dmpe)
. Complexes with sulfur- and oxygen-containing ligands
]
2+
2
in the presence of an excess of
3 2 2 3 2 6 4
composition Tc(PPh ) (CO) [(C H NS)N = CHC H O]. This
toluene-3,4-dithiol (H
[
established by spectroscopic methods and X-ray diffraction
analysis. The coordination polyhedron about technetium is inter-
mediate between the octahedron and the trigonal prism [the Tc7S
2
tdt) gave rise to the thiolate Tc(IV) complex
six-coordinate complex has a distorted octahedral structure with
-3,4).2 Its structure was
55
Tc(tdt)(dmpe) ](PF ) (tdt = MeC
2
6
6
H
3
S
2
3
trans-PPh and cis-CO groups and one chelating bidentate
anion.2
66
Complexes containing biologically active molecules, such as
peptides, proteins or antibodies, as ligands can be used as unique

State-of-the-art coordination chemistry of radioactive elements
879
.
target-specific radiopharmaceuticals in diagnostics. The reaction
7
The [Tc(tu-S)
as the precursor of [Tc(dppe)
phosphinoethane).
6
]Cl
3
4 H
2
O complex (tu-S is thiourea) was used
t
of [TcO
4
]
with SnCl
2
, sodium gluconate and RP 294 produced
2
(Bu NC)
2
](PF
This complex can be prepared by mixing
both ligands and a source of technetium(III) in ethanol followed
by refluxing of the reaction mixture. This procedure is more
convenient than the method involving a sodium amalgam, dppe
6
) (dppe is diphenyl-
the 99Tc(V) oxo complex with RP 294, which exists as the syn and
anti isomers. The study of the crystal structure of the isostructural
rhenium(V) complex demonstrated that the isomerism results
271
from the positions of the CH OH groups in the serine residues.
At room temperature, the isomers in solution undergo intercon-
version. The 9 Tc and rhenium complexes with RP 294 exhibit
2
.
and TcCl
4
(PPh
3
)
2
. In the [Tc(tu-S)
6
]Cl
3
4 H
2
O complex, the
9m
coordination polyhedron about the technetium atom is a distorted
tetrahedron, the isocyanide ligands being in trans positions with
respect to each other.
267
similar chemical properties.
The 99Tc and 99mTc complexes with new tetradentate N
and NS ligands were prepared by refluxing a methanolic solution
of (TcOCl )(NBu ) with the corresponding NS proligands.
The technetium(V) complex [TcO(NS )](NBu ) (48) was obtained
2 2
S
Treatment of [TcO
4
]7 with an excess of the corresponding
2
4
4
3
H
3
S,P-bidentate phosphinothiolate ligands, such as 2-(diphenyl-
phosphino)ethanedithiolate, 2-(diphenylphosphino)propanethio-
late or 2-(diphenylphosphino)thiophenoxide, yielded neutral
technetium(III) complexes.2 These complexes have a trigonal-
bipyramidal geometry, two phosphorus donor centres (consisting
of two chelate rings) occupying axial positions and being in trans
positions with respect to each other.
3
4
in high yield. However, compounds of this type are unstable and
decompose in a matter of several hours or days. By analogy with
the crystal structure of the related rhenium oxo complex, these
compounds can be considered as square-pyramidal complexes
containing the oxygen atom in the apical position.2
72
68
O
5. Complexes with the metal ± metal bond, carbonyl
complexes
The data on complexes containing multiple Tc7Tc bonds are
scarce. Thus several diamagnetic phosphine ditechnetium(II)
S
Tc
S
S
S
1
60
48
2 4 3 4
complexes of the Tc Cl (PR ) type (49) were described.
These complexes contain a triple bond between the metal atoms
and provide the first examples of phosphine complexes possessing
a multiple technetium ± technetium bond.
4. Complexes with phosphorus-containing ligands
Phosphine
99m
Tc-labelled derivatives can be used for obtaining
images of internal organs, for example, heart images. Complexes
PR3
Cl
Tc
Cl
Cl
P
PhMe, 50 ± 55 8C or
PR
3
) (R = Et or Pr) type 234 have distorted
4 3 2
TcCl (PR )
Tc
of the [TcO
trigonal-bipyramidal structures with two oxo ligands located in a
2 3 3 4
(PR ) ](BPh
PhH, PhH, utrasonics Cl
R
3
PR
3
+
single plane. Salts of the [TcO
2
(PR
3
)
3
]
cations are convenient
n
49 (>90%)
starting compounds for the synthesis of other complexes with
mixed ligands.
3
3 3 2 2
PR = PEt , PPr , PMePh , PMe Ph.
2
n�
The polymeric chain structure of [Tc
2
Cl
6
]
n
also contains
Py
triple metal ± metal bonds.273 The triple Tc:Tc bond was found
]+
]+
2 3 2 2
[TcO (PR ) (Py)
[
TcO
2
(PR
3
)
2
74
2 4 2
in the a and b forms of the Tc Cl (dppe)
complex.2 The a
MeOH
isomer 50 adopts an eclipsed conformation; the Tc7Tc distance is
]+ can
be prepared according to a one-pot procedure directly from
2.15(1) A. In the b isomer 51, the twist angle is 35(2) 8 and the
ꢀ
The trimethylphosphine derivative [TcO
2
(PMe
3
)
2
(Py)
2
ꢀ
Tc7Tc distance is 2.117(1) A. These isomeric complexes were
7
pertechnates [TcO
4
] . Apparently, this procedure can be adapted
2 4 3 4 3 3 2
prepared by refluxing Tc Cl (PR ) (PR = PEt or PMe Ph) in
toluene in the presence or in the absence of an excess of dppe,
respectively.
9m
for the preparation of 9 Tc radiopharmaceuticals in hospitals.
Py, PMe
MeOH
3
NH
4
(TcO
4
)
2 3 2 2
[TcO (PMe ) (Py)
]+
L
X
Tc
L
L
X
L
L
L
X
X
Tc
X
Tc
L
Tc
The [TcO
2
(PR
3
)
2
(Py)
2
]+ derivatives are diamagnetic, which is
X
L
X
X
indicative of a noticeable deviation of their geometry from the
ideal octahedron.2
The reactions of pertechnate with derivatives of phosphino-
34
50
51
L = dppe, X = Cl.
carboxylic acids afforded the TcL
phosphino)benzoic acid, 3-(diphenylphosphino)propionic acid or
diphenylphosphino)acetic acid]. According to the results of
3
complexes [L is 2-(diphenyl-
Complexes containing the multiple Tc7Tc bond of order 3.5
were synthesised in high yields by one-electron chemical oxidation
(
spectroscopic studies and X-ray diffraction analysis, these com-
plexes possess a distorted octahedral geometry with the mer
configuration in which the donor atoms of the same type are in
trans positions with respect to each other and the phosphorus
atom is in the trans position with respect to the oxygen atom.2
Complexes of the short-lived 99mTc isotope were prepared
analogously. Their physical and chemical properties are similar to
those of 99Tc complexes. Biological assays revealed significant
brain uptake of these compounds.
of the Tc
phosphate in acetonitrile.2
[Tc Cl (PMe Ph) ](PF
) complex was prepared. 275 Oxidation in
the presence of bis(triphenylphosphine)iminium produced the
2 4 2 4
Cl (PMe Ph) complex with ferrocenium hexafluoro-
75
In this study, the cationic
2
4
2
4
6
69
275
neutral
Tc Cl (PR
Tc
2
Cl
49 (PR
5
(PMe
2
Ph)
= PEt
3
complex.
, PMePh or PMe
The
complexes
Ph) reacted with
2
4
3
)
molten diphenyl- or di-p-tolylformamidine to give mixtures of
4
3
3
2
2
formamidine-bridged complexes of the general formula
2 4 n
(L) Cl
(n = 1 or 2) in moderate yields.2 Complexes with
76
Tc
the triple Tc:Tc bond, for example [Tc
an acetonitrile solution can undergo photodissociation to give the
2
77
Chelate technetium(V) complexes with bis(o-hydroxyphenyl)-
phenylphosphine and (o-hydroxyphenyl)diphenylphosphine were
prepared by metathesis of the corresponding Tc(V) precursors or
by reduction ± ligand exchange with ammonium pertechnate.2
These complexes combine a soft phosphine donor site and two
hard phenoxide centres. It was expected that this fact would
stabilise technetium in intermediate oxidation states.
2
(MeCN)10](BF
4
)
4
,
in
2+
278
[Tc(MeCN)
6
]
ions in almost quantitative yields. A decaace-
70
tonitrile binuclear complex with the triple Tc:Tc bond was
obtained in good yield by acidification of a solution of
Tc
2 4 3 4
Cl (PR ) in a mixture of acetonitrile and dichloromethane
.
277
n7
using HBF
4
Et
2
O.
The [Tc
2
Cl
8
]
(n = 2, 3 or 4) and

8
80
B I Kharisov, M A Mendez-Rojas
m7
[
Mo
methods.
Of other types of Tc complexes, noteworthy are Tc carbonyl
derivatives.280 ± 282 The Tc(CO)
I complex, which is isostructural
to the Mn(CO) I complex, exists as orthorhombic crystals. Its
crystal structure consists of Tc(CO) I molecules. The crystals of
are monoclinic and are also built of individual
molecules. Complexes with composition
(M = Mn, Tc or Re; X = Cl, Br or I) are isostruc-
2
Cl
8
]
(m = 4 or 5) clusters were studied by theoretical
practical use and theoretical interest. Thus considerable recent
attention has been given to bimetallic complexes of 5f elements in
connection with a search for new unusual properties and molec-
ular structures. Investigations and a search for new uranium(V)
279
5
1
66, 167
5
complexes remain to be of great importance. Information
on the unique activities of alkylcyclopentadienyl derivatives
5
Ã
[
[
[
Tc(CO)
Tc(CO)
4
4
I]
I]
2
Cp AnR
2
2
(An = Th or U; R = H or Alk) as catalysts of alkene
hydrogenation and polymerisation gave impetus to studies in this
field of chemistry. These compounds proved to be ten times more
2
4 2
M(CO) X]
tural. The main types of technetium complexes are given in
Table 9.
2
active than traditional Pt/SiO catalysts. Hence, actinide com-
plexes are of interest from the viewpoint of extension of the scope
of their use in catalysis, as the starting compounds in organo-
17, 24
*
*
*
metallic synthesis
actinides.2
and for separation and extraction of
83
In spite of the difficulties associated with operations with radio-
active elements, their complexes are being studied intensively. The
development of the coordination chemistry of these compounds,
particularly, of those containing radioactive elements in unusual
oxidation states,24 is dictated both by the possibility of their
We are grateful to Professor M Ephritikhine (Service de
Chimie Moleculaire, France) for permission to reproduce schemes
from his articles and Professors A D Garnovskii (Rostov State
University, Russia) and S S Berdonosov (Moscow State Univer-
sity, Russian Federation) for valuable advice.
Table 9. Synthesis of technetium complexes with oxygen-, sulfur-, nitrogen- and phosphorus-containing ligands.
Starting compound
Reagent and reaction conditions
Products
Ref.
257
Complexes with oxygen- and sulfur-containing ligands
But
But
OH, MeOH
OH
CH=N(CSNC
KTcO
4
Tc(DBCat)
3
2
, Tc(DBCat) (DBAP)
.
Tc(PPh
3
)
2
(CO)
3
Cl
LiOC
6
H
4
3
H
2
), THF
Tc(PPh
(C
3
)
2
(CO)
2
266
282
[
3
H
2
NSC)N=CHC
6
H
4
O]
5
X
H
2
O
3 2 3
[Tc(CO) (H O)
]+
Tc(CO)
X = Cl, Br, I)
Complexes with nitrogen-containing ligands
(
II
(see a)
Tc
(
2
Cl
4
(PR
3
)
4
(1) Bu
3
SnH or Zn
[Tc (MeCN)10](BF
4
4
)
)
4
4
277
277
2
PR
3
= PEt
3
,
(2) MeCN, HBF
4
PMe
2 2
Ph, PMePh )
[
TcCl
6
]2
7
(1) Bu
3
SnH or Zn
[Tc (MeCN)10](BF
II
2
(
2) MeCN, HBF
4
(
Bu
4
N)(TcOCl
4
)
Cys b
HTcO(Cys)
2
258
237
t
3
t
TcCl
3
(PPh (MeCN)
3
)
2
Bu (tpy), DME
TcCl
3
[Bu (tpy)]
3
1
2
NH
4
TcO
4
, MeOH
TcCl
3
(Z -NNC
5
H
4
NH)(Z -HNNC
5
H
4
N)
238
.
N
NHNH
2
HCl
Complexes with phosphorus-containing ligands
Tc Cl (PMe Ph) (Cp Fe)(PF
NH (TcO PR , MeOH
R = Et, Pr) (see d)
PR , MeOH, Py
(R = Et, Pr)
2
4
2
4
2
6
)
[Tc
2
Cl
4
(PMe
2
Ph)
4
](PF
6
) c
275
234
4
4
3
)
)
3
[TcO
2
(PR
3
)
)
3
3
]+
(
[
TcO
2
(PR
3
]+
3
[TcO
2
(PR
3
3
(Py)
2
]+
234
(
R = Et, Pr)
TcCl
3
(PPh
3
3
)
2
2
(MeCN)
TMEDA, PhMe, DME
TcCl
mer-TcCl
TcCl (PR
Tc Cl (PEt
3
(PPh
)
2
(TMEDA)
237
241
160
160
Py
3 2
(Py)
n
TcCl
TcCl
4
4
(PPh
)
PR
3
(R = Et, Pr ), THF
4
3 2
)
(PEt
3
)
2
Zn, PhH, utrasonics
2
4
3 4
)
a
The yield was 50%, the Tc7Tc multiple bond is present; Cys is an aqueous solution of cysteine chloride monohydrate; c the multiple Tc7Tc bond is
b
d
present; the yield was 60% ± 70%; a *10-fold excess of the ligand was used; there was no need for the use of reducing agents; the reaction was
3
accompanied by the formation of NH .

State-of-the-art coordination chemistry of radioactive elements
881
3
8. A J Zozulin, D C Moody, R R Ryan Inorg. Chem. 21 3083 (1981)
9. J L Stewart, R A Andersen J. Chem. Soc., Chem. Commun. 1846
1987)
References
3
(
1
. Metody Elementoorganicheskoi Khimii. Lantanidy i Aktinidy
Methods of Organoelement Chemistry. Lanthanides and
4
0. L R Avens, D M Barnhart, C J Burns, S D McKee, W H Smith,
Inorg. Chem. 33 4245 (1994)
(
Actinides) (Eds N A Nesmeyanov, K A Kocheshkov) (Moscow:
Khimiya, 1974)
4
1. N Edelstein J. Less-Common Met. 133 39 (1987)
2. C Baudin, D Baudry, M Ephritikhine J. Organomet. Chem. 415 59
4
2
3
4
. T J Marks, R D Ernst, in Comprehensive Organometallic Chemistry
Vol. 3 (Eds D Wilkinson, F G Stone, E W Abel) (Oxford: Pergamon
Press, 1982) p. 173
(1991)
3. R G Jones, E Bindschadler, D Blume, G Karmas, G A Martin Jr,
J R Thirtle, F A Yeoman, H Gilman J. Am. Chem. Soc. 78 6030
4
. T J Marks, V W Day, in Fundamental and Technological Aspects of
Organo-f Element Chemistry (Eds T J Marks, I L Fragala)
(
4. F A Cotton, G Wilkinson, C A Murillo, M Bochmann Advanced
1956)
4
4
4
4
(Dordrecht: Reidel, 1985) p. 115
Inorganic Chemistry (New York: Wiley, 1999)
5. T Arliguie, D Baudry, M Ephritikhine, M Nierlich, M Lance,
J Vigner J. Chem. Soc., Dalton Trans. 1019 (1992)
. J Takats, in Fundamental and Technological Aspects of Organo-f
Element Chemistry (Eds T J Marks, I L Fragala) (Dordrecht:
Reidel, 1985) p. 159
6. D L Clark, J C Huffman, J G Watkin J. Chem. Soc., Chem.
Commun. 266 (1992)
5
6
. I Santos, A Pires de Matos, A G Maddock Adv. Organomet. Chem.
3
4 65 (1989)
. B E Bursten, R J Strittmatter Angew. Chem., Int. Ed. Engl. 30 1069
1991)
7. D M Barnhart, D L Clark, J C Gordon, J C Huffman, J G Watkin,
B D Zwick Inorg. Chem. 34 5416 (1995)
(
4
8. R C Mehrotra, A Singh, U M Tripathi Chem. Rev. 91 1287 (1991)
9. W G van der Sluys, C J Burns, J C Huffman, A P Sattelberger,
J. Am. Chem. Soc. 110 5924 (1988)
7
. NATO ASI Ser., Partnership Sub-Ser. 2, Environ. 41 (1998)
. D J Cardin (Ed.) Organometallic Compounds of the Lanthanides,
Actinides, and Early Transition Metals (London: Chapman and Hall,
4
8
5
5
5
0. D M Barnhart, T M Frankcom, P L Gordon, N N Sauer,
J A Thompson, J G Watkin Inorg. Chem. 34 4862 (1995)
1. W G van der Sluys, J C Huffman, D S Ehler, N N Sauer Inorg.
Chem. 31 1316 (1992)
1
985)
9
. D N Suglobov, G V Sidorenko, E K Legin, in Letuchie Organi-
cheskie i Kompleksnye Soedineniya f-Elementov (Volatile Organic and
Complex Compounds of the f Elements) (Moscow: Energoatomizdat,
2. B A Vaartstra, J C Huffman, P S Gradeff, L G Hubert-Pfalzgraf,
J-C Daran, S Parraud, K Yunlu, K G Caulton Inorg. Chem. 29 3126
1987) p. 208
1
1
1
1
0. K Schwochau, U Pleger Radiochim. Acta 63 103 (1993)
1. C E Housecroft Coord. Chem. Rev. 162 305 (1997)
2. F S Schoster, S K Zeisler J. Rad. Nucl. Chem. 220 149 (1997)
3. N M Vanlic-Razumenic, T N Maksin, L P Vuksanovic J. Serb.
Chem. Soc. 60 641 (1995)
(
1990)
53. C H Winter, P H Sheridan, M J Heeg Inorg. Chem. 30 1962 (1991)
54. D L Clark, J G Watkin Inorg. Chem. 32 1766 (1993)
55. J M Berg, A P Sattelberger, D E Morris, W G van der Sluys,
P Fleig Inorg. Chem. 32 647 (1993)
1
1
1
1
4. C E Housecroft Coord. Chem. Rev. 142 21 (1995)
5. E C Constable, C E Housecroft Coord. Chem. Rev. 131 153 (1994)
6. U Mazzi Polyhedron 8 1683 (1989)
5
6. T Arliguie, D Baudry, J C Berthet New J. Chem. 15 569 (1991)
7. L K Templeton, D H Templeton, N Bartlett, K Seppelt Inorg.
Chem. 15 2720 (1976)
5
7. G L Soloveichik, in Encyclopedia of Inorganic Chemistry Vol. 1
5
8. S D McKee, C J Burns, L R Avens Inorg. Chem. 37 4040 (1998)
9. P Roussel, P B Hitchcock, N D Tinker, P Scott Inorg. Chem. 36
(
Ed. R B King) (New York: Wiley, 1994) p. 2
8. An N Nesmeyanov Radiokhimiya (Radiation Chemistry)
Moscow: Khimiya, 1978)
5
1
1
5
716 (1997)
0. M R Duttera, V W Day, T J Marks J. Am. Chem. Soc. 106 2907
1984)
(
6
6
6
6
6
6
9. M S S Brooks, B Johansson, H L Skriver, in Handbook on the
Physics and Chemistry of the Actinides Vol. 1 (Eds A J Freeman,
G H Lander) (Amsterdam: North-Holland, 1984) Pt. 3, p. 153
0. D L Clark, A P Sattelberger, in Encyclopedia of Inorganic
Chemistry Vol. 1 (Ed. R B King) (New York: Wiley, 1994) p. 19
1. L T Reynolds, G Wilkinson J. Inorg. Nucl. Chem. 2 246 (1956)
2. J H Burns, in The Chemistry of Actinide Elements Vol. 2
(
1. D L Clark, S D Conradson, D W Keogh, P D Palmer, B L Scott,
C D Tait Inorg. Chem. 37 2893 (1998)
2. A Anderson, C Chieh, D E Irish, J P K Tong Can. J. Chem. 58 1651
2
(
1980)
3. A Coda, A Dell Giusta, V Tazzoli Acta Crystallogr., Sect. B 37 1496
1981)
4. R Graziani, G Bombieri, E Forsellini J. Chem. Soc., Dalton Trans.
059 (1972)
2
2
(
(Eds J J Katz, G T Seaborg, L R Morris) (London: Chapman and
Hall, 1986) p. 1417
2
2
2
2
2
2
2
2
3
3. D Kepert Inorganic Stereochemistry (Berlin: Springer, 1982)
4. M Ephritikhine New J. Chem. 16 451 (1992)
5. C J Burns, B E Bursten Comments Inorg. Chem. 9 61 (1989)
6. P Pyykkoe, L L Lohr Jr Inorg. Chem. 20 1950 (1981)
5. M S Grigor'ev, I G Tananaev, N N Krot, A I Yanovskii,
Yu T Struchkov Radiokhimiya 39 325 (1997) a
6
6
6
6
7
7
7
7
6. J Bruno, I Grenthe, P Robouch Inorg. Chim. Acta. 158 221 (1989)
7. L B Serezhkina, V N Serezhkin Radiokhimiya 38 117 (1996) a
8. L B Serezhkina, V N Serezhkin Zh. Neorg. Khim. 41 427 (1996) b
9. L B Serezhkina, V N Serezhkin Zh. Neorg. Khim. 41 438 (1996) b
0. L B Serezhkina, V N Serezhkin Koord. Khim. 22 786 (1996) c
1. C J Dodge, A J Francis Environ. Sci. Technol. 31 3062 (1997)
2. M T H Tarafder, A R Khan J. Indian Chem. Soc. 74 489 (1997)
3. M Bhattacharjee, M K Chaudhuri, R N D Purkoyastha J. Chem.
Soc., Dalton Trans. 2883 (1990)
4. S A Kulyukhin, N B Mikheev Radiokhimiya 39 127; 130 (1997) a
5. C S Tellez, J Gomez-Lara Spectrochim. Acta. 51A 395 (1995)
6. C S Tellez, J Gomez-Lara, M A Mondragdn, V M CastaKho,
G R Mena Vib. Spectrosc. 9 279 (1995)
7. N Ro
È
sch, A Streitwieser Jr J. Am. Chem. Soc. 105 7237 (1983)
sch Inorg. Chim. Acta. 94 297 (1984)
8. N Ro
È
9. A H H Chang, R M Pitzer J. Am. Chem. Soc. 111 2500 (1989)
0. S Ahrland, in The Chemistry of Actinide Elements Vol. 2
(Eds J J Katz, G T Seaborg, L R Morris) (London: Chapman and
Hall, 1986) p. 1480
3
1. I Grenthe, J Fuger, R J M Konings, R J Lemire, A B Muller,
C Nguyen-Trung, H Wanner, H Forest, in Chemical Thermo-
dynamics of Uranium (Eds H Wanner, I Forest) (Amsterdam:
Elsevier, 1992) p. 193
7
7
7
3
2. J Fuger, in Plutonium Chemistry (American Chemical Society,
Symposium Series) (Eds W T Carnall, G R Choppin) Vol. 216;
7
7. I A Charushnikova, A Yu Garnov, V P Perminov, A A Bessonov,
N N Krot Radiokhimiya 40 302 (1998) a
(Washington, DC: American Chemical Society, 1983) p. 74
3
3
3
3. P G Allen, J J Bucher, D K Shuh, N M Edelstein, T Reich Inorg.
Chem. 36 4676 (1997)
7
7
8. C A Tellez-Sara, J Gomez-Lara J. Braz. Chem. Soc. 7 505 (1996)
9. C A Tellez-Sara, M Arissawa, J Gomez-Lara, M A Mondragdn
Polyhedron 19 2353 (2000)
4. H Moll, M A Denecke, F Jalilehvand, M Sanstro
Inorg. Chem. 38 1795 (1999)
5. A Plyasunov, T Fanghanel, I Grenthe Acta Chem. Scand. 52 250
1998)
È
m, I Grenthe
8
8
8
0. J Gomez-Lara, Bol. Inst. Quim. UNAM 16 27 (1964)
1. L Matassa, N Kumar, D G Tuck Inorg. Chim. Acta. 109 19 (1985)
2. N N Kostyuk, T A Kolevich, V L Shirokii, D S Umreiko Koord.
Khim. 15 1704 (1989) c
(
3
6. S Basak, D Banerjea Indian J. Chem., Sect. A 32 129 (1993)
7. W G van der Sluys, A P Sattelberger Chem. Rev. 90 1027 (1990)
3

8
82
B I Kharisov, M A Mendez-Rojas
8
8
8
3. N N Kostyuk, V L Shirokii, I I Vinokurov, N A Maier
Zh. Obshch. Khim. 64 1432 (1994) d
4. Direct Synthesis of Coordination and Organometallic Compounds.
128. K G Moloy, T J Marks J. Am. Chem. Soc. 106 7051 (1984)
129. K G Moloy, T J Marks Inorg. Chim. Acta. 110 127 (1985)
130. K Tatsumi, A Nakamura, P Hoffman, P Stauffert, R Hoffmann
J. Am. Chem. Soc. 107 4440 (1985)
(
Eds A D Garnovskii, B I Kharisov) (Amsterdam: Elsevier, 1999)
5. R L Belford, A E Martell, M Calvin J. Inorg. Nucl. Chem. 14 169
1960)
131. J-F Le Marechal, M Ephritikhine, G Folcher J. Organomet. Chem.
299 85 (1986)
(
8
8
8
8
9
6. D C Bradley, M A Saad, W Wardlaw J. Chem. Soc. 1091 (1954)
7. A G Maddock, A Pires de Matos Radiochim. Acta. 18 71 (1972)
8. E T Samulski, D G Karraker J. Inorg. Nucl. Chem. 29 993 (1967)
9. S D McKee, C J Burns, L R Avens Inorg. Chem. 37 4040 (1998)
0. D L Clark, S K Grumbine, B L Scott, J G Watkin
132. J H Burns, P G Laubereau Inorg. Chem. 10 2789 (1971)
133. J Goffart, S Bettonville J. Organomet. Chem. 361 17 (1989)
134. D Baudry, M Ephritikhine, F Nief, L Ricard, F Mathey Angew.
Chem., Int. Ed. Engl. 29 1485 (1990)
135. T Arliguie, M Lance, M Nierlich, J Vigner, M Ephritikhine
J. Chem. Soc., Chem. Commun. 183 (1995)
Organometallics 15 949 (1996)
1. D C Bradley, B Harder, F Hudswell J. Chem. Soc. 3318 (1957)
2. W G van der Sluys, C J Burns, A P Sattelberger Organometallics 8
9
136. J C Green, N Kaltsoyannis, K H Sze, M MacDonald J. Am.
Chem. Soc. 116 1994 (1994)
9
8
55 (1989)
3. A Vallat, E Laviron, A Dormond J. Chem. Soc., Dalton Trans. 921
1990)
137. A R Schake, L R Avens, C J Burns, D L Clark, A P Sattelberger,
W H Smith Organometallics, 12 1497 (1993)
9
(
138. C Boisson, J C Berthet, M Ephritikhine J. Chem. Soc., Dalton
Trans. 947 (1996)
9
9
9
4. J G Brennan, R A Andersen, A Zalkin Inorg. Chem. 25 1756 (1986)
5. S D Stults, R A Andersen, A Zalkin Organometallics 9 1623 (1990)
'
6. J-C J Berthet, J F Le Marechal, M Lance, M Nierlich, J Vigner,
139. A F England, C J Burns, S L Buchwald Organometallics 13 3491
(1994)
M Ephritikhine J. Chem. Soc., Dalton Trans. 1573 (1992)
7. L A Avens, S G Bott, D L Clark, A P Sattelberger, J G Watkin,
B D Zwick Inorg. Chem. 33 2248 (1994)
140. B Kanellakopulos, E Dornberger, F Baumgarther Inorg. Nucl.
Chem. Lett. 10 155 (1974)
9
9
9
141. C-H Wong, T Yen, T Lee Acta Crystallogr. 18 340 (1965)
142. M Weydert, J G Brennan, R A Andersen, R G Bergman
Organometallics 14 3942 (1995)
8. D L Clark, A P Sattelberger, S G Bott, R N Vrtis Inorg. Chem. 28
1771 (1989)
9. J Drozdzyuski, J G H Du Preez Inorg. Chim. Acta. 218 203 (1994)
143. G Paolucci, G Rosserto, P Zanella, R G Fischer J. Organomet.
Chem. 284 213 (1985)
1
00. L R Avens, D M Barnhart, C J Burns, S D McKee Inorg. Chem.
5 537 (1996)
01. W G van der Sluys, J M Berg, D Barnhardt Inorg. Chim. Acta. 204
51 (1993)
3
144. F Ossola, G Rosserto, P Zanella, G Paolucci J. Organomet. Chem.
309 55 (1986)
1
1
2
145. M Porchia, N Brianese, U Casellato, F Ossola, G Rosserto,
P Zanella, R Graziani J. Chem. Soc., Dalton Trans. 677 (1989)
146. P Zanella, N Brianese, U Casellato, F Ossola, M Porchia,
G Rossetto, R Graziani J. Chem. Soc., Dalton Trans. 2039 (1987)
147. M R Leonov, N I Gramoteeva, V A Il'yushenkov,
L A Pogodina Radiokhimiya 42 210 (2000) a
02. J G H Du Preez, L Gouws, H Rohwer, B J A M van Brecht,
B Zeelie, U Casellato, R Graziani J. Chem. Soc., Dalton Trans.
2585 (1991)
1
03. J G H Du Preez, H E Rohwer, B J A M van Brecht, H Zeelve,
U Casellato, R Graziani Inorg. Chim. Acta. 189 67 (1991)
04. J G H Du Preez, B Zeelie Inorg. Chim. Acta. 161 187 (1989)
05. L Arnaudet, R Bougon, B Buu, M Lance, M Nierlich, J Vinger
Inorg. Chem. 33 4510 (1994)
1
1
148. H Lauke, P N Swepston, T J Marks J. Am. Chem. Soc. 106 6841
(1984)
149. T Arliguie, M Lance, M Ephritikhine J. Chem. Soc., Dalton Trans.
2501 (1997)
1
1
1
1
1
06. D C Moody, J D Odom J. Inorg. Nucl. Chem. 41 533 (1979)
07. S J Simpson, R A Andersen J. Am. Chem. Soc. 103 4063 (1981)
08. N Kumar, D G Tuck Inorg. Chem. 22 1951 (1983)
09. G B Deacon, T D Tuong Polyhedron 7 249 (1988)
10. D M Barnhart, D L Clark, S K Grumbine, J G Watkin Inorg.
Chem. 34 1695 (1995)
150. T R Boussie, D C Eisenberg, J Rigsbee, A Streitwieser, A Zalkin
Organometallics 10 1922 (1991)
151. A Streitwieser, M T Barros, H K Wang, T R Boussie
Organometallics 12 5023 (1993)
152. D G Karraker, A Stone J. Am. Chem. Soc. 96 6885 (1974)
153. D G Karraker J. Inorg. Nucl. Chem. 39 87 (1977)
154. T M Gilbert, R R Ryan, A P Sattelberger Organometallics 8 857
(1989)
1
11. R J Butcher, D L Clark, S K Grumbine, B L Scott, J G Watkin
Organometallics 15 1488 (1996)
1
1
1
12. R A Andersen Inorg. Chem. 18 1507 (1979)
13. R S Sternal, T J Marks Organometallics 6 2621 (1987)
14. B Kanellokopulos, E O Fischer, E Dornberger, F Baumgartner
J. Organomet. Chem. 24 507 (1970)
155. A R Achake, L R Avens, C J Burns, D L Clark, A P Sattelberger,
W H Smith Organometallics 12 1497 (1993)
156. J Ogden, in Cryochemistry (Eds M Moskovitz, G A Ozin)
(New York: Wiley, 1976) Ch. 7, p. 146
1
1
1
15. D Baudry, E Bulot, M Ephritikhine J. Chem. Soc., Chem.
Commun. 1316 (1989)
16. C Clappe, D Hauchard, G Durand J. Electroanal. Chem. 448 95
157. C Villiers, M Ephritikhine J. Chem. Soc., Dalton Trans. 3397 (1994)
158. B C Ankianies, P E Fanwick, I P Rothwell J. Am. Chem. Soc. 113
4710 (1991)
(1998)
'
17. J-F Le Marechal, C Villers, P Charpin, M Lance, M Nierlich,
159. R Adam, C Villiers, M Ephritikhine New J. Chem. 17 455 (1993)
160. A Hafid, A Dormond, D Baudry New J. Chem. 18 557 (1994)
161. R R Ryan Inorg. Chim. Acta. 162 221 (1989)
162. D Baudry, E Bulot, M Ephritikhine J. Chem. Soc., Chem.
Commun. 1369 (1988)
J Vigner, M Ephritikhine J. Chem. Soc., Chem. Commun. 308
(1989)
1
18. J G Brennan, S D Stults, R A Andersen, A Zalkin Inorg. Chim.
Acta. 139 201 (1987)
1
1
1
19. B E Bursten, R J Strittmatter J. Am. Chem. Soc. 109 6606 (1987)
20. J E Ellis, W Beck Angew. Chem. 34 2489 (1995)
21. S Di Bella, A Gulino, G Lanza, I L Fragala J. Phys. Chem. 97
163. D Rabinovich, R M Chamberlin, B L Scott, J B Nielsen,
K D Abney Inorg. Chem. 36 4216 (1997)
164. D L Clark, J G Watkin, S K Grumbine J. Am. Chem. Soc. 117
9089 (1995)
11673 (1993)
1
22. A C Gulina, S Di Bella Organometallics 11 3248 (1992)
23. M Spirlet, J Rebizant, C Apostolidis, E Dornberger,
B Kanellakopulos, B Powietzka Polyhedron 15 1503 (1996)
24. X Jemine, J Goffart, P C Leverd J. Organomet. Chem. 469 55
165. D Rabinovitch, C M Haswell, B L Scott, R L Miller, J B Nielsen,
K D Abney Inorg. Chem. 35 1425 (1996)
'
166. J-C Berthet, J-F Le Marechal, M Ephritikhine J. Chem. Soc.,
1
1
1
1
1
Chem. Commun. 360 (1991)
167. S M Cendrowski-Guillaume, M Ephritikhine J. Chem. Soc.,
Dalton Trans. 1487 (1996)
(1994)
25. P C Blake, M F Lappert, J L Atwood, H Zhang J. Chem. Soc.,
Chem. Commun. 1436 (1988)
26. S Di Bella, G Lanza, I L Fragala, T J Marks Organometallics 15
168. F M De Rege, W H Smith, B L Scott, J B Nielsen, K D Abney
Inorg. Chem. 37 3664 (1998)
205 (1996)
169. O Bilsel, S N Milam, G S Girolami, K S Suslick, D Holten
J. Phys. Chem. 97 7216 (1993)
27. W K Kot, G V Shalimov, N M Edelshtein, M A Edelman,
M F Lappert J. Am. Chem. Soc. 110 986 (1988)

State-of-the-art coordination chemistry of radioactive elements
883
1
1
1
70. B I Kharisov, M A Mendes-Roias, F A Ganich Koord. Khim. 26
23 (2000) c
71. M K Engel Rep. Nakamura Inst. Chem. Res., Vol. Date 1996 8 11
1997)
214. S J Coles, A A Danopoulos, P W Read J. Chem. Soc., Dalton
Trans. 3401 (1995)
3
215. K Aparna, S S Krishnamurthy, M Nethaji J. Chem. Soc., Dalton
Trans. 2991 (1995)
(
72. B Nartsissov, US Department of Commerce, Aerospace
Technology Division, Library of Congress, Washington, DC, Rep.
No AD 629515 (Microfilm) (1966)
216. A Vasilescu-Saidel, C N Turcanu, R Grosescu J. Radioanal. Nucl.
Chem. 203 177 (1996)
217. A Vasilescu-Saidel, C N Turcanu, R Grosescu J. Radioanal. Nucl.
Chem. 203 189 (1996)
1
1
1
1
1
73. A L Thomas Phthalocyanines. Research and Application (Boca
Raton, FL: CRC Press, 1990)
74. K L Raymond, G E Freeman, M J Kappel Inorg. Chim. Acta 94
218. R Arad-Yellin, M Zangen, H Gottlieb J. Chem. Soc., Dalton Trans.
2081 (1990)
1
93 (1984)
75. Y-D Z Han, S-Y Ying-Jie Niu Sci. China., Ser. B, Chem., Life Sci.
6 1061 (1993)
219. T L Novoderezhkina, A F Borina, B N Kulikovskii
Koord. Khim. 22 797 (1996) c
3
220. M R Duttera, P J Fagan, T J Marks, V W Day J. Am. Chem. Soc.
104 865 (1982)
76. M G Lappert, P P Power, A R Sanger, R C Srivastava Metal and
Metalloid Amides (New York: Wiley, 1980)
221. H J Wasserman, D C Moody, R R Ryan J. Chem. Soc., Chem.
Commun. 532 (1984)
77. J C Berthet, C Boisson, M Lance, J Viegner, M Nierlich,
M Ephritikhine J. Chem. Soc., Dalton Trans. 3019 (1995)
78. P Roussel, P Hitchcock, B P Scott Inorg. Chem. 36 5716 (1997)
79. A Zalkin, J G Brennan, R A Andersen Acta Crystallogr., Sect. C.
222. H J Wasserman, D C Moody, R T Paine, R R Ryan, K V Salazar
J. Chem. Soc., Chem. Commun. 533 (1984)
1
1
223. R E Cramer, S Roth, J W Gilje Organometallics 8 2327 (1989)
224. P C Leverd, M Lance, M Ephritikhine J. Chem. Soc., Dalton
Trans. 3563 (1994)
43 418; 421 (1987)
1
80. S E Turman, W G van der Sluys Polyhedron 11 3139 (1992)
81. C J Burns, D C Smith, A P Sattelberger, H B Gray Inorg. Chem.
1
225. T Arliguie, M Fourmique, M Ephritikhine Organometallics 19 109
(2000)
31 3724 (1992)
1
1
1
1
82. Yu N Mikhailov, Yu E Gorbunova, V N Serezhkin Dokl. Akad.
Nauk, Ser. Khim. 358 360 (1998)
226. K Tatsumi, I Matsubara, Y Inoue, A Nakamura, R E Cramer,
G J Tagoshi, J A Golen, J W Gilje Inorg. Chem. 29 4928 (1990)
227. P C Leverd, M Lance, M Ephritikhine J. Chem. Soc., Dalton
Trans. 237 (1995)
È
83. M Muller, V C Williams, L H Doerrer, M A Leech, S A Mason,
M L H Green, K Prout Inorg. Chem. 37 1315 (1998)
84. R Wietzke, M Mazzanti, J Pecaut J. Chem. Soc., Dalton Trans.
228. I A Charushnikova, N N Krot, Z A Starikova Radiokhimiya 42
397 (2000) a
4087 (1998)
85. J-C Berthet, Ch Boisson, M Ephritikhine J. Chem. Soc., Dalton
Trans. 3027 (1995)
229. P C Leverd, T Arliguie, M Lance J. Chem. Soc., Dalton Trans. 501
(1994)
186. P Scott, P B Hitchcock J. Chem. Soc., Dalton Trans. 603 (1995)
187. J-C Berthet, M Ephritikhine Coord. Chem. Rev. 178 83 (1998)
188. D S J Arney, C J Burns J. Am. Chem. Soc. 117 9448 (1995)
189. R E Cramer, K Panchanatheswaran, J W Gilje J. Am. Chem. Soc.
230. P C Leverd, T Arliguie, M Ephritikhine New J. Chem. 17 769
(1993)
231. T Arliguie, M Fourmigue, M Ephritikhine Organometallics 19 109
(2000)
1
06 1853 (1984)
232. L Bahadur, J P Pandey J. Electrochem. Soc. 137 3755 (1990)
233. P C Leverd, M Lance, M Nierlich, J Viegner, M Ephritikhine
J. Chem. Soc., Dalton Trans. 2251 (1993)
1
90. J G Brennan, R A Andersen J. Am. Chem. Soc. 107 514 (1985)
91. A L Odom, P L Arnold, C C Cummins J. Am. Chem. Soc. 120
1
5
836 (1998)
92. G P Kushto, P F Souter, L Andrews J. Chem. Phys. 108 7121
1998)
93. T Straub, W Frank, M S Eisen J. Chem. Soc., Dalton Trans. 2541
1996)
234. F D Rochon, R Melanson, P-C Kong Inorg. Chem. 37 87 (1998)
235. S Baum, R Bramlet Basic Nuclear Medicine (New York:
Appleton-Century-Crofts, 1975)
1
1
1
1
(
236. Radiopharmaceuticals (Eds G Subramanian, B A Rhodes,
J F Cooper, V J Sodd) (New York: The Society of Nuclear
Medicine, 1975)
(
94. A Cassol, P Di Bernardo, R Portanova, M Tolazzi, G Tomat,
P Zanonato Inorg. Chem. 29 1079 (1990)
237. J Barrera, A K Burrel, J C Bryan Inorg. Chem. 35 335 (1996)
238. D J Rose, K P Maresca, T Nicholson, A Davison, A G Jones,
J Babich, A Fischman, W Graham, J R D DeBord, J Zubieta
Inorg. Chem. 37 2701 (1998)
95. D R Brown, R G Denning, R H Jones J. Chem. Soc., Chem.
Commun. 2601 (1994)
96. R G Denning Struct. Bond. 79 215 (1992)
1
1
97. L R Morss, W T Carnall, C W Williams J. Less-Common Met. 169
239. M J Abrams, S K Larsen, S N Shalkh, J Zubieta Inorg. Chim.
Acta 185 7 (1991)
1
98. P Scott, P B Hitchcock J. Chem. Soc., Chem. Commun. 579 (1995)
(1991)
1
1
240. M Hirsch-Kuchma, T Nicholson, A Davison, W M Davis,
A G Jones Inorg. Chem. 36 3237 (1997)
99. V S Koltunov, E A Mezhov, S M Baranov Radiokhimiya 42 65
(
2000) a
241. J Lu, A Yamano, M J Clarke Inorg. Chem. 29 3483 (1990)
242. A Marchi, R Rossi, L Magon, A Duatti, U Casellato, R Graziani,
M Vidal, F Riche J. Chem. Soc., Dalton Trans. 1935 (1990)
243. C M Archer, J R Dilworth, D V Griffiths, M McPartlin,
J D Kelly J. Chem. Soc., Dalton Trans. 183 (1992)
244. A Marchi, L Marvelli, R Rossi, L Magon, V Bertolasi, V Ferretti,
P Gilli J. Chem. Soc., Dalton Trans. 1485 (1992)
245. J Baldas, J F Boas, S F Colmanet, G A Williams J. Chem. Soc.,
Dalton Trans. 2845 (1992)
2
2
2
00. O V Mikhailov Radiokhimiya 40 316 (1998) a
01. M R Maurya, R C Maurya Rev. Inorg. Chem. 15 1 (1995)
02. A M El-Hendawy, A El-Kourashy, M M El-Ghany Shanab
Polyhedron 11 523 (1992)
2
03. A Syamal, M M Singh Indian J. Chem., Sect. A, Inorg. 37 350
(
1998)
2
2
2
2
04. A Syamal, M M Singh Indian J. Chem., Sect. A, Inorg. 31 110 (1992)
05. A H Amrallah Pak. J. Sci. Ind. Res. 37 231 (1994)
06. A Syamal, M M Singh React. Polym. 21 149 (1993)
07. I V Khudyakov, N J Turro, I K Yakushenko J. Photochem.
Photobiol. 63 25 (1992)
246. C Bolzati, L Uccelli, A Duatti, M Venturini, C Morin,
'
S Cheradame, F Refosco, F Ossola, F Tisato Inorg. Chem. 36 3582
(1997)
2
08. D L Clark, J G Watkin, R J Butcher Organometallics, 14 2799 (1995)
09. M D Fryzuk, T S Haddad, D J Berg Coord. Chem. Rev. 99 137
247. U Abram, E S Lang, S Aram, J Wegmann, J R Dilworth,
R Kirmse, J D Woollins J. Chem. Soc., Dalton Trans. 623 (1997)
248. M Cattabriga, A Marchi, L Marvelli, R Rossi, G Vertuani,
R Pecoraro, A Scattarin, V Bertolasi, V Ferretti J. Chem. Soc.,
Dalton Trans. 1453 (1998)
2
(
1990)
10. P G Edwards, P A Andersen, A Zalkin J. Am. Chem. Soc. 103 7792
1981)
2
(
2
2
11. P G Edwards, J S Parry, P W Reed Organometallics 14 3649 (1995)
12. S G Deshpande, S C Jain Indian J. Chem., Sect. A, Inorg. 30 549
249. A K Burrell, D L Clark, P L Gordon, A P Sattelberger,
J C Bryan J. Am. Chem. Soc. 116 3813 (1994)
250. J G Du Preez, T I A Gerber, M L Gibson J. Coord. Chem. 22 33
(1990)
(
1991)
13. M Nierlich, P Gradoz, M Ephritikhine J. Organometal. Chem. 481
9 (1994)
2
6
251. J Barrera, J C Bryan Inorg. Chem. 35 1825 (1996)

8
84
B I Kharisov, M A Mendez-Rojas
2
52. C M Archer, J R Dilworth, P Jobanputra, R M Thompson,
M McPartlin, W Hiller J. Chem. Soc., Dalton Trans. 897 (1999)
53. E N Treher, L C Francesconi, J Z Gougoutas, M F Malley,
A D Nunn Inorg. Chem. 28 3411 (1989)
2
2
2
2
2
2
2
2
2
54. C M Archer, J R Dilworth, R M Thompson, M McPartlin,
D C Povey, J D Kelly J. Chem. Soc., Dalton Trans. 461 (1993)
55. T Konno, J R Kirchhoff, M J Heeg, W R Heineman, E Deutsch
J. Chem. Soc., Dalton Trans. 3069 (1992)
56. E Shuter, H R Hoveyda, V Karunaratne, S J Rettig, C Orvig
Inorg. Chem. 33 368 (1996)
57. L A de Learie, R C Haltiwangen, C G Pierpont J. Am. Chem. Soc.
111 4324 (1989)
58. M Chatterjee, B Achari, S Das, R Banerjee, C Chakrabarti,
J K Dattagupta, S Banerjee Inorg. Chem. 37 5424 (1998)
59. N Bryson, J C Dewan, J Lister-James, A G Jones, A Davison
Inorg. Chem. 27 2154 (1988)
60. N Bryson, J Lister-James, A G Jones, W M Davis, A Davison
Inorg. Chem. 29 2948 (1990)
61. A Yokoyama, H Saji, H Tanaka, T Odori, R Morita, T Mori,
K Torizuka J. Nucl. Med. 17 810 (1976)
2
62. I Ikeda, O Inoue, K Kurata J. Nucl. Med. 18 1223 (1977)
63. W Brandau, B Bubeck, M Eisenhut, D M Taylor Appl. Radiat.
Isot. 39 121 (1988)
2
2
2
2
2
64. M Chattopadhyay, K N Jalan, A K Pal, S N Benerjee Nucl. Med.
Biol. 15 535 (1988)
65. L G Marzilli, M G Banaszcyk, L Hansen, Z Kuklenyik, R Cini,
A Taylor Inorg. Chem. 33 4850 (1994)
66. R Rossi, A Marchi, L Magon, A Duatti, V Casellato, R Graziani
Inorg. Chim. Acta 160 23 (1989)
67. E Wong, T Fauconnier, S Bennett, J Valliant, T Nguyen, F Lau,
L F L Lu, A Pollak, R A Bell, J R Thornback Inorg. Chem. 36
5799 (1997)
2
68. C M Archer, J R Dilworth, D V Griffithi, M J Al-Jebbori,
J D Kelly, C Lu, M J Rosser, Y Zheng J. Chem. Soc., Dalton
Trans. 1403 (1997)
2
2
2
2
2
2
2
2
2
2
69. F Refosco, F Tisato, G Bandoli, E Deutsch J. Chem. Soc., Dalton
Trans. 2901 (1993)
70. H Luo, I Setyawati, S J Rettig, C Orvig Inorg. Chem. 34 2287
(
1995)
71. L Kaden, A J L Pombeiro, Y Wang, U Abram Inorg. Chim. Acta
30 189 (1995)
2
72. F Tisato, F Refosco, G Bandoli, C Bolzati, A Moresco J. Chem.
Soc., Dalton Trans. 1453 (1994)
73. F A Cotton, L M Daniels, L R Falvello, M S Grigoriev,
S V Kryuchkov Inorg. Chim. Acta 189 53 (1991)
74. F A Cotton, L M Daniels, S C Haefner, A P Sattelberger Inorg.
Chim. Acta 288 69 (1999)
75. F A Cotton, S C Haefner, A P Sattelberger Inorg. Chem. 35 1831
(
1996)
76. F A Cotton, S C Haefner, A P Sattelberger Inorg. Chem. 35 7350
1996)
(
77. J C Bryan, F A Cotton, L M Daniels, S C Haefner,
A P Sattelberger Inorg. Chem. 34 1875 (1995)
78. F A Cotton, S C Haefner, A P Sattelberger J. Am. Chem. Soc. 118
5486 (1996)
2
2
79. Yu V Plekhanov, S V Kryuchkov Radiokhimiya 39 210 (1997) a
80. M S Grigor'ev, A E Miroslavov, G V Sidorenko,
D N Suglobov Radiokhimiya 39 204 (1997) a
2
2
2
81. M S Grigor'ev, A E Miroslavov, G V Sidorenko,
D N Suglobov Radiokhimiya 39 207 (1997) a
82. N I Gorshkov, A A Lumpov, A E Miroslavov, D N Suglobov
Radiokhimiya 42 213 (2000) a
83. S S Travnikov, E V Fedoseev, A V Davydov, B F Myasoedov, in
Teoreticheskaya i Prikladnaya Khimiya b-Diketonatov Metallov
(Theoretical and Applied Chemistry of Metal b-Diketonates )
(Eds V I Spitsyn, L I Martynenko) (Moscow: Nauka, 1985) p. 224
a
b
c
Ð Radiochemistry (Engl. Transl.)
Ð Russ. J. Inorg. Chem. (Engl. Transl.)
Ð Russ. J. Coord. Chem. (Engl. Transl.)
Ð Russ. J. Gen. Chem. (Engl. Transl.)
Ð Dokl. Chem. (Engl. Transl.)
d
e