Extraction and coordination studies of the unexplored bifunctional ligand carbamoyl methyl sulfoxide (CMSO) with uranium(VI) and cerium(III) nitrates. Synthesis and structures of [UO2(NO3) 2(PhSOCH2CONi</su

Article abstract of DOI:10.1039/b407824a

The bifunctional carbamoyl methyl sulfoxide ligands, PhCH ₂SOCH₂CONHPh (L₁), PhCH₂SOCH ₂CONHCH₂Ph (L₂), PhSOCH₂CON ⁱPr₂ (L₃), PhSOCH

Full text of DOI:10.1039/b407824a

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F U L L P A P E R
Extraction and coordination studies of the unexplored bifunctional
ligand carbamoyl methyl sulfoxide (CMSO) with uranium(VI) and
cerium(III) nitrates. Synthesis and structures of [UO (NO ) (PhSO-
2
3 2
i
CH CON Bu )] and [Ce(NO ) (PhSOCH CONBu ) ]†
2
2
3 3
2
2 2
a
a
a
Shanmugaperumal Kannan,* Kuna Venugopal Chetty, Venkatarama Venugopal and
b
Michael G. B. Drew*
a
Fuel Chemistry Division, Bhabha Atomic Research Center, Mumbai 400085, India.
E-mail: skannan@magnum.barc.ernet.in; Fax: (+ 91) 22 25505151
School of Chemistry, The University of Reading, P.O. Box 224, Whiteknights, Reading,
b
UK RG6 6AD. E-mail: m.g.b.drew@reading.ac.uk
Received 24thaM yy20ꢀcceA4edpꢁ4ꢂeA4eꢃbeꢄ yy2
Fiꢄꢁ4Aꢅbꢆiꢁtedaꢁasꢀdvasceꢀꢄ4icꢆeꢇs4teꢈebpꢉ4tꢂeA4eꢃbeꢄ yy2
The bifunctional carbamoyl methyl sulfoxide ligands, PhCH
2
SOCH
), PhSOCH CON Bu
have been synthesized and characterized by spectroscopic methods. The selected coordination chemistry of
, L , L and L with [UO (NO ] and [Ce(NO ] has been evaluated. The structures of the compounds
UO (NO (PhSOCH )] (10) and [Ce(NO (PhSOCH CONBu ] (12) have been determined by single
crystal X-ray diffraction methods. Preliminary extraction studies of ligand L with U(VI), Pu(IV) and Am(III) in
tracer level showed an appreciable extraction for U(VI) and Pu(IV) in up to 10 M HNO but not for Am(III). Thermal
2
CONHPh (L
1
), PhCH
2
SOCH
2
CONHCH
2
Ph
6
)
i
i
(L
2
), PhSOCH
2
CON Pr
2
(L
3
), PhSOCH
2
CONBu
2
(L
4
2
2
(L
5
) and PhSOCH
2
CON(C
8
H
17
)
2
(L
L
[
1
3
4
5
2
3
)
2
3 3
)
i
2
3
)
2
2
CON Bu
2
3
)
3
2
2 2
)
6
3
studies on compounds 8 and 10 in air revealed that the ligands can be destroyed completely on incineration. The
electron spray mass spectra of compounds 8 and 10 in acetone show that extensive ligand distribution reactions
occur in solution to give a mixture of products with ligand to metal ratios of 1:1 and 2:1. However, 10 retains its
2 2
solid state structure in CH Cl .
1
Introduction
series, the coordination and extraction chemistry of bifunctional
ligands containing the SO–CO groups [Fig. 1(f)] has not yet been
studied, though the extraction and coordination chemistry of
The coordination chemistry of neutral bifunctional carbamoyl
methyl phosphonates (CMP), carbamoyl methyl phosphine
oxides (CMPO) and malonyl diamides (MDA) [Fig. 1(a)–(c)]
with the lanthanide and actinide ions is very important for
understanding the nature of species extracted during the
solvent extraction separation of these ions from acid media.
The extraction and coordination properties of these bi-
functional ligands are distinctly different from those of the
monofunctional organophosphonates, phosphine oxides and
amides. Extensive studies on the coordination chemistry of
CMP, CMPO and malonyl diamide types of ligands with the
lanthanide and actinide ions; have been reported to characterize
the steric and electronic features that influence the ligand bind-
ing to the metal ions. In these studies, bifunctional ligands
containing combinations of PO–CO (CMP or CMPO), PO–SO
6
7
monofunctional sulfoxides and amides are well established.
Trifunctional ligands8 containing two carbamoyl and one
sulfoxide groups have been reported and show excellent extrac-
tion properties for actinide ions. These trifunctional ligands are
not analogous to either CMP or CMPO. We, report herein, our
studies on the syntheses, coordination and extraction abilities
of a bifunctional ligand, carbamoyl methyl sulfoxide (CMSO)
with Ce(III), U(VI), Pu(IV) and Am(III) ions.
1
–3
3–5
4
5
2
Results and discussion
The reaction of benzyl thioacetic acid with aniline or benzyl
amine and monochloroacetyl amides with thiophenol yielded
the corresponding thioamides. These thioamides on oxidation
with SeO /H O yielded the corresponding carbamoyl methyl
(
b-sulfoxo phosphine oxide), PO–NO (b-N-oxo phosphine
2
2
2
oxide) and CO–CO (malonamides) [Fig. 1(a)–(e)] groups as
a neutral donor centers have been reported. However, in this
1 6 1 6
sulfoxides L to L (Scheme 1). The IR spectra of L –L showed
1
the presence of both carbamoyl and sulfoxide groups. The H
NMR spectra of L –L showed the expected peak multiplicities
and integrations. The SOCH CO protons of all these ligands
1
6
2
showed a doublet of doublet pattern due to the diastereotopic
nature of these protons. However, the corresponding thioamides
showed a single resonance for the same protons.
2
.1 Complexation study of L
1
, L
3
, L
4
and L
5
with uranyl nitrate
with uranyl
The complexing ability of L
1
, L
3
, L
4
and L
5
nitrate was studied by using elemental analysis, IR and NMR
spectroscopic techniques. The reaction of [UO (NO ·6H O]
with L , L , L or L , yielded the compounds 7–10 (Scheme 1).
2
3
)
2
2
1
3
4
5
The C, H, N analysis revealed that the ratio of ligand to
uranyl nitrate is 1:1 in all these compounds. The IR spectra of
Fig. 1 Structures of different types of bifunctional extractants.
7
–10 show that the water molecules of the starting compound
†
Electronic supplementary information (ESI) available: TG/DTA for
6
and 10, ES-MS for 8 and 10 in acetone, 10 in CH Cl , logD vs. log[L ]
[
UO (NO ·6H O] are completely replaced by these ligands
2
3
)
2
2
8
2
2
and that the ligands are bonded through both the sulfoxo and
carbamoyl oxygen atoms to the uranyl group. The observed
plots for Pu(IV) and U(VI) and powder XRD patterns of the decomposed
products of 8 and 10. See http://www.rsc.org/suppdata/dt/b4/b407824a/
3
6 0 4
D a l t o n T r a n s . , 2 0 0 4 , 3 6 0 4 – 3 6 1 0
T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 4

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Table 1 Important bond distances (Å) and angles (°) for 10 and 12
1
0
U1–O100
U1–O200
U1–O51
U1–O61
S2–O1
1.747(8)
1.759(9)
2.554(9)
2.520(12)
1.502(10)
U1–O1
2.442(9)
2.408(9)
2.514(10)
2.513(10)
1.259(13)
U1–O15
U1–O52
U1–O62
C14–O15
O100–U1–O200
O52–U1–O51
O62–U1–O1
O100–U1–O1
O100–U1–O15
179.3(5)
50.2(3)
62.4(4)
90.1(4)
97.1(4)
O1–U1–O15
O61–U1–O62
O15–U1–O51
O200–U1–O1
O200–U1–O15
70.3(3)
50.5(4)
66.3(3)
90.5(4)
83.4(4)
1
2
Scheme 1
frequency differences for the sulfoxo (DmSO = 30–60 cm ),
and carbamoyl (DmCO = 35–50 cm ) groups agree well with
the supposition that the sulfoxo or carbamoyl groups are
bonded to the uranyl group directly in the reported compounds.
Ce1–O31
Ce1–O35
Ce1–O11
Ce1–O12
Ce1–O71
S32–O31
2.496(10)
2.511(9)
2.732(6)
2.660(19)
2.619(12)
1.551(12)
O31–Ce1–O71
O35–Ce1–O71
137.7(4)
81.7(4)
75.3(3)
179.3(6)
72.4(5)
68.5(4)
−
1
4h,9
a
O35 –Ce1–O71
−
1
4,5
O11–Ce1–O11a
O31–Ce1–O12a
O35–Ce1–O12a
O31–Ce1–O31a
66.9(5)
135.0(3)
70.0(3)
154.8(4)
141.2(5)
79.3(5)
106.7(5)
71.3(5)
68.7(5)
O71–Ce1–O12a
125.7(5)
72.4(5)
86.4(5)
117.5(4)
68.5(4)
154.7(6)
72.6(5)
108.9(5)
112.0(5)
Similar difference are also observed in the compounds of CMP
a
a
i
O31 –Ce1–O35
O31 –Ce1–O12
or CMPO with the uranyl nitrate such as, [UO
2
(NO
CONEt
3
)
2
{( PrO)
2
2
-
O31–Ce1–O35
O31–Ce1–O12
O35–Ce1–O12
4
a
4d
POCH
UO (NO
it seems apparent that ligands L
2
CONEt
2
}],
[UO
2
(NO
SO(p-MeC
, L
3
)
2
(Ph
2
POCH
2
)]
)}] and therefore
, L and L are acting
or
a
O35–Ce1–O35
i
4i
[
2
3
)
2
{( PrO)
2
POCH
2
6
H
4
O31–Ce1–O71a
a
O35 –Ce1–O12
O12 –Ce1–O12
a
1
3
4
5
O71–Ce1–O12
a
as bidentate chelating ligands in compounds 7–10, in a
O31 –Ce1–O11
O31–Ce1–O11
a
1
O35–Ce1–O11
O71–Ce1–O11
O12–Ce1–O11
O35 –Ce1–O11
similar fashion to those of CMP or CMPO. The H NMR
a
O71 –Ce1–O11
2
spectra of 7–10 show that the CH protons are deshielded by
133.5(5)
ca 0.8–1.3 ppm with respect to the free ligands and support the
coordination of these ligands to the uranyl group. The struc-
ture of the compound 10 has been determined by single crystal
X-ray diffraction methods and confirms these conclusions.
a
Symmetry element −x, y, 1.5 − z.
i
6 4 2 3 2
H (NO ) -
)}]4i or [UO
[
UO
2
(NO
NCO)
U–O(sulfoxide) (2.442(9) Å) in 10 is close to the values observed
3
)
2
{( PrO)
CH }].
2 2
2
POCH
2
SO(p-MeC
i
5g
2
.2 Molecular structure of 10
{( Pr
2
The observed bond distance for
The molecular structure of 10 is shown in Fig. 2 and selected
interatomic bond distances and angles are given in Table 1. The
structure shows that the uranium atom is surrounded by eight
oxygen atoms in a hexagonal-bipyramidal geometry. The four
oxygen atoms of the two nitrate groups and the two oxygen
atoms of the CMSO ligand forms the equatorial hexagonal
plane. The two uranyl oxygen atoms occupy the axial positions.
The CMSO ligand acts as a bidentate chelating ligand and is
bonded through both the sulfoxo and amido oxygen atoms to
the uranyl group.
i
4i
in [UO
UO (DBM)
PhSOPh)] (2.427(6) Å) and [UO
2
(NO
3
)
2
{( PrO)
SOMe)] (2.375(6) Å), [UO
(DBM) (PhCH SOCH
2
POCH
2
SO(p-MeC
6
H
4
)}] (2.36(2) Å),
[
2
2
(PhCH
2
2
(DBM)
2
-
(
(
2
2
2
2
Ph)]
10
2.421(6) Å). The U–O(amide) distance (2.408(9) Å) is
comparable in magnitude with that of the values observed in
[
(
(
UO
2
(NO
(Ph
NCOCH
3
)
2
2
{Ph(EtO)POCH
2
CONEt
2
}] (2.426(8) Å), [UO
2
-
-
4d
NO
3
)
2
POCH
2
2
CONEt
2
)] (2.404(5) Å) and [UO (NO )
2 3
2
i
i
5g
Pr
2
2
CON Pr )] (2.41(2) Å). The angles subtended
at the metal atom show that the uranium atom has a slightly
distorted hexagonal-bipyramidal geometry. The seven atoms
This is a similar type of coordination to that observed in
the compounds of CMP, CMPO, b-sulfoxo phosphine oxide
UO
6
in the equatorial plane show an rms deviation of 0.12 Å
from the least squares plane.
or malonamide with uranyl nitrate such as, [UO
EtO)POCH CONEt }], [UO (NO (Ph POCH
2
(NO
CONEt )],
3 2
) {Ph-
4
d
(
2
2
2
3
)
2
2
2
2
2
3 4 5
.3 Complexation study of L , L and L with cerium(III)
nitrate
3 4 5 3 3 2
The reaction of L , L or L with [Ce(NO ) ·6H O] yielded 11,
1
2 or 13 (Scheme 1). The C, H, N analysis of 11–13 revealed
that the ratio of ligand to cerium(III) nitrate is 2:1 in all the
three compounds. The IR spectra of 11–13 show that the
3 3 2
water molecules of the starting compound [Ce(NO ) ·6H O]
are replaced completely by these ligands and also that the
ligands are bonded through both the sulfoxo and carbamoyl
oxygen atoms to the cerium atom (DmSO = 24–47 cm−1 and
−
1
DmCO = 41–53 cm ). This observation is similar to that
observed in the compounds of CMPO, CMP or malonamide
-
3 3
with lanthanide(III) nitrate compounds such as [Gd(NO )
i
4h
{
( PrO)
2
POCH
2
SO(p-MeC
6
H
4
)}
2
],
[Ce(NO
3
)
3
(TMSA)
2
]
or
5
e
[
Ce(NO
3
)
3
(TMSA) ]
2 ∞
and clearly suggests that the CMSO
ligands in compounds 11–13 behave in a similar manner
to that of the more familiar CMPO, CMP or malonamide
1
ligands. The H NMR spectra of the compounds show that
2
the CH protons of the CMSO ligands are deshielded by ca.
Fig. 2 Molecular structure of 10 (hydrogen atoms omitted for
clarity).
1.7–2.1 ppm with respect to the free ligands providing further
evidence for the coordination of CMSO ligands to the cerium
D a l t o n T r a n s . , 2 0 0 4 , 3 6 0 4 – 3 6 1 0
3 6 0 5

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ion. The structure of the compound 12 has been determined
by single crystal X-ray diffraction methods and confirms our
interpretation of the spectral data.
2
.4 Molecular structure of 12
The molecular structure of 12 which has crystallographic C
2
symmetry is shown in Fig. 3 together with the numbering
scheme and selected interatomic bond distances and angles
are given in Table 1. The structure shows that the cerium(III)
ion is bonded to two CMSO and three nitrate ligands to give
a coordination number of ten. Both CMSO ligands act as
bidentate chelating ligands and are bonded through both the
sulfoxo and amido oxygen atoms to the cerium(III) nitrate. Six
oxygen atoms from three nitrate groups and four oxygen atoms
from two CMSO ligands form a bicapped square-antiprismatic
geometry around the cerium atom. This type of structure is
also observed in compounds of CMP, CMPO or bis(diphenyl-
phosphinomethane) dioxide with lanthanide(III) nitrates, viz;
6
Fig. 4 Extraction data for L with U(VI), Pu(IV) and Am(III).
i
4b
[
Sm(NO
3
)
3
{( PrO)
2
POCH
2
CONEt
2
}
2
], [Nd(NO
3
)
3
(Ph
2
POCH
2
11
-
concentrations of 1–10 M. However, Am(III) shows much less
extraction under the conditions studied. The observed distribu-
tion ratios follow the order of: DPu(IV) > DU(IV)  DAm(III), and are
similar to those observed for the CMP, CMPO or malonamide
4
e
CONEt
2
)
2
]
and [M(NO
3
)
3
(DPPMO)
2
] (M = La or Ce).
The observed metal–oxygen bond lengths are in the range of
1
1
5e
2
.62–2.73 Å for Ce–O(nitrate), 2.511(9) Å for Ce–O(amide)
4
h,12
1k
and 2.496(10) Å for Ce–O(sulfoxo),
those found previously.
values which agree well
ligands with these metal ions. Extraction for Am(III) was
improved for these ligands by suitably modifying the groups
around the donor atoms and diluents14 and similar studies are
in progress for the CMSO ligands.
In order to establish the nature of species extracted during
the solvent extraction process, the distribution ratios for U(IV)
and Pu(IV) were measured as a function of CMSO concentra-
tions. The plot of logD vs. log[CMSO] for U(IV) and Pu(IV)
show straight lines with slopes close to 2 (1.83 and 2.2 for
the U(VI) and Pu(IV), respectively, see ESI†). These studies
show clearly that the nature of species extracted under these
solvent extraction conditions are [UO
2 3 2
(NO ) ·2CMSO] and
[
Pu(NO ·2CMSO], respectively, for U(VI) and Pu(IV). This
3 4
)
observation is similar to that observed for CMP or CMPO
with U(VI) and Pu(IV) ions.1 However, the malonamide shows
either 2:1 or 3:1 complex formation with the Pu(IV) ion.2
e,j
e,15
2
.6 Stripping studies
Stripping studies on U(VI) and Pu(IV) extracted from higher
HNO concentrations (5–10 M) were carried out using dilute
nitric acid to assess the feasibility of back extraction for these
ions. Both the uranium (0.1 M HNO ) and plutonium (0.35 M
HNO or 1 M HNO –0.2 M ascorbic acid) were stripped
3
Fig. 3 Molecular structure of 12 (hydrogen atoms omitted for
clarity).
3
3
3
quantitatively from an organic layer (75 and 85%, respectively,
for uranium and plutonium in a single contact and >99% on
further stripping for about two to three times). These studies
show clearly that the uranium and plutonium can be extracted
even from very high acid concentration up to 10 M and stripped
2
.5 Thermal studies of the compounds 8 and 10
Thermogravimetric (TG) and differential thermal analyses
(
DTA) of 8 and 10 were carried out to find out the product
of the decomposition reaction. These compounds decompose
in four to five steps to give U as a final product (identified
back quantitatively by using dilute HNO
needed very strong stripping agents e.g. Na
phosphonic acids to obtain an equivalent result.
3
. However, the CMPO
3
O
8
2
CO , oxalic or
3
from the powder X-diffraction pattern of the decomposition
product), without any other impurities. However, the decom-
position product of phosphine oxides compounds of uranyl
nitrate yielded the corresponding uranyl phosphate as a final
product. This observation clearly shows that the CMSO
ligands can be completely destroyed on incineration, as indeed
2.7 Electron spray mass spectrometric studies on compounds 8
and 10
1
3
The solvent extraction study of CMSO with U(IV) revealed that
the species extracted has a ligand to metal ratio of 2 :1. How-
ever, the solid-state structure of the complex isolated shows a
2
a,g
can the amide ligands.
ligand to metal ratio of 1:1. Similar results were also reported
2
.6 Extraction studies of U(VI), Pu(IV) and Am(III) with L
6
for the CMP, CMPO and malonamide ligands.1
,2,4,5
In order to
from nitric acid medium
establish the nature of the complexes formed in solution, the
electron spray mass spectra1 for complexes 8 and 10 were
measured in acetone. The m/z values and the corresponding
compounds identified are listed in Table 2. It shows clearly
that extensive ligand distribution reaction occurs in acetone to
give a mixture of products with ligand to metal ratios of 1:1
and 2:1. The formation of both 1:1 and 2:1 compounds have
also been reported for the malonamide–uranyl nitrate4 and
1,16
The extraction studies were carried out by using the ligand L
in toluene with U(VI), Pu(IV) and Am(III) in tracer level (using
6
2
33
241
the U, Pu and Am tracers) from nitric acid medium to
assess feasibility of using these ligands for extraction purposes.
Distribution ratios (D) for U(VI) and Pu(IV) and Am(III) as a
function of nitric acid concentration (Fig. 4) shows clearly that
U(VI) and Pu(IV) are extracted significantly from nitric acid at
g,17
3
6 0 6
D a l t o n T r a n s . , 2 0 0 4 , 3 6 0 4 – 3 6 1 0

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Table 2 Electron spray mass spectral data for 8 and 10 in acetone
solution on evaporation yielded a white powder, which was
recrystallized from hot ethanol as a white solid. yield: 8.8 g
8
10
(
82%). Calc. (%) for PhCH
2 2 2
SOCH CONHPh, C15H15SNO : C
6
5.9, H 5.5, N 5.1. Found: C 65.8, H 5.5, N 5.0; IR (KBr, Nujol
Ion
m/z
Ion
m/z
−
1
1
mull): m/cm 3176, 3121 (NH), 1671 (CO), 1020 (SO) ; H NMR
CDCl ): d 3.311 (d, 1H, 13 Hz, OS–CH –CO), 3.734 (d, 1H,
13 Hz, OS–CH –CO), 4.214 (q, 2H, 6 Hz, CH OS–), 7.13–7. 56
(m, 5H, Ph), 9.1 (br, 1H, NH).
(
3
2
[
[
[
[
[
UO
UO
UO
UO
UO
2
2
2
2
2
(NO
(NO
(NO
3
3
3
)L
)(H
)L]
2
]+
2
866.5
617.1
599.3
537.3
270.1
[UO
[UO
[UO
[UO
[UO
2
2
2
2
2
2
2
2
(NO
(NO
(NO
3
3
3
)L
)L(H
)L]
2
]+
922.6
645.4
627.4
565.4
439.1
430.3
300.5
270.1
O)L]+
O)]+
2
2
2
+
+
+
+
L]
L]
+
]2+
L]2+
]
(H
2
O)L
2
3.4 Synthesis of benzyl N-benzylcarbamoylmethyl sulfoxide
(L )
2
L
2
]2
+
[
[
[
UO
UO
UO
(H
]
2
O)
2
+
This was prepared similarly to 1 by taking benzyl thioacetic
acid (10 g, 0.055 mol) and benzyl amine (10 mL). The inter-
2 2 2
mediate product PhCH SCH CONHCH Ph was isolated as a
malonamide–lanthanide nitrate5b compounds. The ion found
in the solid-state structure is not observed but its occurrence
pale yellow liquid (yield: 12.5 g, 84%) and was used as such
without any purification for further reaction with H O /SeO
2
2
2
is indicated by the presence in low concentration of the
2 2 2
(yield: 13.2 g, 89%). Calc. (%) for PhCH SOCH CONHCH Ph,
+
cation [UO
2
L(NO
3
)] . While the solid-state structure of 10 is
16 17 2
C H SNO : C 66.9, H 5.9, N 4.9. Found: C 66.7, H 5.8, N
−
1
not observed in acetone, it is observed in CH
2
Cl
2
as demon-
4.9; IR (KBr, Nujol mull): m/cm 3233 (NH), 1640–1620
1
strated by the occurrence of peaks at m/z of 692 [M + 2H +
(CO), 1033 (SO); H NMR (CDCl ): d 3.219 (d, 1H, 13 Hz,
3
+
H , 100% (breaking of the S–CH
2
bond followed by addition
OS–CH –CO), 3.563 (d, 1H, 13 Hz, OS–CH –CO), 4.089 (q,
2
2
+
+
of 2H and one H )] and 613 [M − Ph + H , 53% (breaking of
the S–Ph bond followed by addition of H )] (see ESI†).
2 2
2H, 6 Hz, CH SO–), 4.520 (m, 2H, NCH ), 7.26–7.38 (m, 6H,
Ph + NH).
+
3
Experimental
3.5 Synthesis of N,N-diisopropylcarbamoylmethyl phenyl
sulfoxide (L
3
)
3
.1 Materials
To a solution of thiophenol (6.2 g, 0.056 mol) in ethanol,
All starting materials and other chemicals were reagent grade
and were commercially available. The starting compounds
sodium hydroxide (2.4 g, 0.06 mol) was added and stirred
i
for 10 min. To this solution, ClCH
2
CON Pr
2
(10 g, 0.56 mol)
i
i
ClCH
CON(C
2
CON Pr
2 2 2 2 2 2
, ClCH CON Bu , ClCH CONBu and ClCH -
was added slowly with stirring and the solution precipitated
NaCl immediately. The whole solution was then refluxed
for 2 h and evaporated to dryness. The resulting solid was
extracted with chloroform (50 mL) and washed with 20%
1
8
8
17 2
H )
were prepared according to literature methods.
The FTIR spectra were obtained on a JASCO-610 FTIR
spectrometer and the samples were mounted as Nujol
1
mulls. The H NMR in CDCl
3
or acetone-d
6
for ligands
Na
dried over anhydrous Na
evaporation yielded a pale yellow viscous liquid, identified as
2
CO
3
solution (2 × 20 mL). The chloroform solution was
and compounds were recorded on Bruker 300 or 500 MHz
spectrometers. Elemental analyses were performed by the
Analytical Chemistry Division of Bhabha Atomic Research
Centre, Mumbai. The TG/DTA for 8 and 9 were recorded on
a Seteram or Mettler instrument under a flow of air/oxygen
atmosphere.
2
SO and filtered. This filtrate on
4
i
1
2 2
PhSCH CON Pr from the H NMR, IR, carbon, hydrogen
and nitrogen analyses (yield: 13.5 g, 92%). This compound
was used for further reaction without any further purification.
i
PhSCH
2
CON Pr
2
(13 g, 0.52 mol) was dissolved in 50 mL of
(5.9 mL of
(5.75 g, 0.052 mol)
methanol and added slowly to a solution of H
0% H solution, 0.052 mol) and SeO
2 2
O
3
.2 Electron spray mass spectra
3
2
O
2
2
The electron spray ionization mass spectrometric detection of
positive ions was performed using a MICROMASS-Q-TOF
MICRO instrument. The samples were introduced in to the
source with the syringe pump. Nitrogen was employed as both
the drying and spraying gas with at source temperature of 90 °C.
The cone voltage was set to 30 V, the voltage applied on the
capillary was 1162 kV and the sample solution flow rate was
in methanol (50 mL) with stirring. The solution was stirred for
2 h and added slowly to a saturated NaCl solution (100 mL)
with stirring. The solution was allowed to stand overnight and
deposited a white crystalline solid, which was filtered off and
washed with water (5 × 100 mL) and dried. It was recrystallized
from a chloroform–dodecane mixture as a white crystalline
i
solid (yield: 12.3 g, 89%). Calc. (%) for PhSOCH
2
CON Pr
2
,
−
1
5
lL min . Spectra were recorded from m/z of 50 to 2000.
14 2
C H21SNO : C 62.9, H 7. 9, N 5.2. Found: C 62.7, H 7.8, N
−
1
1
5
.0; IR (KBr, Nujol): m/cm 1642 (CO), 1038 (SO); H NMR
(CDCl ): d 1.04, 1.16, 1.25, 1.34 (d, 6 Hz, 12H, CH ), 3.48 (m,
1H, NCH), 3.70 (d, 1H, 14 Hz, SO–CH –CO), 3.85 (m, 1H,
–CO), 7.25–7.52 (m, 3H,
3
.3 Synthesis of benzyl N-phenylcarbamoylmethyl sulfoxide
3
3
(
L
1
)
2
NCH), 4.03 (d, 1H, 14 Hz, SO–CH
Ph), 7.73–7.76 (m, 2H, Ph).
2
Aniline (10 mL) was added to solid benzylthioacetic acid
10 g, 0.055 mol) and heated for 4 h at 130–140 °C. The
resulting liquid was added slowly with stirring to a 20% HCl
100 mL) solution. The resulting light brown colored solid
formed was filtered off, washed with water and dried. It was
(
3
.6 Synthesis of N,N-dibutylcarbamoylmethyl phenyl
(
sulfoxide (L
4
)
1
identified as PhCH
2
SCH
2
CONHPh from the IR, H NMR,
4 3 2 2
L was prepared similarly to L by taking ClCH CONBu
carbon, hydrogen and nitrogen analysis (yield: 13.0 g, 92%).
This solid (8.3 g, 0.032 mol) was suspended in 100 mL of
(11.2 g) and thiophenol (6 g). The product was obtained as a
highly viscous liquid and was found to decompose on heating
under vacuum (yield: 14 g, 92% based on the sulfite used).
methanol and slowly added to a solution of H
0% H solution, 0.032 mol) and SeO (3.58 g, 0.032 mol)
in methanol (50 mL) with stirring. The solution became
2 2
O (3.7 mL of
3
2
O
2
2
Calc. (%) for PhSOCH
2 2 2
CONBu , C16H25SNO : C 65.1, H 8.5,
1
9
−1
N 4.7. Found: C 64. 8, H 8.2, N 5.0 ; IR (KBr, Nujol): m/cm
1
clear and on further stirring deposited a white product. The
whole solution was stirred further for 2 h and saturated with
1637 (CO), 1047 (SO); H NMR (CDCl
CH ), 1.21 (m, 4H, CH ), 1.42 (m, 4H, CH
NCH ), 3.25 (m, 2H, NCH ), 3.71 (d, 1H, 14 Hz, SO–CH
2
3
): d 0.85–0.96 (m, 6H,
), 3.05–3.16 (m, 2H,
–CO),
2
–CO), 7.30–7.52 (m, 3H, Ph),
3
2
2
2
0% NaCl (100 mL) solution. The solution was allowed to
stand overnight and the solid was extracted with chloroform
50 mL × 3), dried over anhydrous Na SO and filtered. The
2
2
4.03 (d, 1H, 14 Hz, SO–CH
7.73–7.75 (m, 2H, Ph).
(
2
4
D a l t o n T r a n s . , 2 0 0 4 , 3 6 0 4 – 3 6 1 0
3 6 0 7

View Article Online
3
.7 Synthesis of N,N-diisobutylcarbamoylmethyl phenyl
NCH
SO–CH
8
2
), 3.76 (br, 1H, NCH
–CO), 5.04 (br, 1H, SO–CH
.00 (m, 2H, Ph).
2
), 4.06 (br, 1H, NCH
2
), 4.97 (br, 1H,
sulfoxide (L
5
)
2
2
–CO), 7.76 (m, 3H, Ph),
i
L
5
was prepared similarly to L
3 2 2
by taking ClCH CON Bu
(
13 g) and thiophenol (7 g). The product was obtained as a
3
2 3 2 5
.12 Synthesis of [UO (NO ) (L )] (10)
highly viscous liquid which was found to decompose on heat-
ing under vacuum (yield: 14.5 g, 92% based on the sulfite).
This was prepared similarly to 8 by taking L
2.0 mmol) and [UO (NO ·6H O] (502 mg, 1.0 mmol). The
final product was recrystallized from hot CH ClCH Cl–
dodecane as a yellow crystalline solid (yield, 610 mg, 89%).
5
(580 mg,
i
Calc. (%) for PhSOCH
2
CON Bu
2
, C16
H
25SNO
2
: C 65.1, H 8.5,
2
3
)
2
2
−
1
N 4.7. Found: C 65.0, H 8.3, N 4.9; IR (KBr, Nujol): m/cm
2
2
1
1
636 (CO), 1047 (SO); H NMR (CDCl
CH ), 0.80 (d, 4 Hz, 6H, CH ), 0.85 (d, 4 Hz, 3H, CH
m, 6 Hz, 1H, CH), 1.92 (m, 7 Hz, 1H, CH), 2.98 (m, 2H,
NCH ), 3.14 (m, 2H, NCH ), 3.77 (d, 1H, 14 Hz, SO–CH
3
): d 0.78 (d, 4 Hz, 3H,
i
3
3
3
), 1.78
Calc. (%) for [UO
2 3 2 2 2 3
(NO ) PhSOCH CON Bu ], C16H25SN O10U:
(
C 27.9, H 3.6, N 6.1. Found: C 27.7, H 3.2, N 5.8; IR (KBr,
−
1
1
2
2
2
–
Nujol): m/cm 1594 (CO), 1011 (SO); 940 (OUO); H NMR
(CD COCD ): d 0.86 (d, 7 Hz, 3H, CH ), 0.88 (d, 7 Hz, 6H,
CH ), 0.91 (d, 6 Hz, 6H, CH ), 2.11 (m, 6 Hz, 1H, CH), 2.18 (m,
Hz, 1H, CH), 3.48 (br, 1H, NCH ), 3.57 (br, 1H, NCH ), 3.72
(br, 1H, NCH ), 4.01 (br, 1H, NCH ), 5.11 (br, 1H, SO–CH
CO), 5.15 (d, 1H, 14 Hz, SO–CH
CO), 4.09 (d, 1H, 14 Hz, SO–CH
Ph), 7.76 (m, 2H, Ph).
2
–CO), 7.31–7. 50 (m, 3H,
3
3
3
3
3
6
2
2
3
.8 Synthesis of N,N-dioctylcarbamoylmethyl phenyl
2
2
2
–
sulfoxide (L
6
)
2
–CO), 7.72–7.77 (m, 3H, Ph),
8
.11 (br, 2H, Ph).
L
(
6
was prepared similarly to L
30 g) and thiophenol (10.4 g). The product was obtained as a
light yellow liquid (yield: 35 g, 93% based on the sulfite used).
Calc. (%) for PhSOCH CON(C : C 70.8, H
0.5, N 3.5. Found: C 70.0, H 10.1, N 3.4; IR (KBr, Nujol):
3 2 8 17 2
by taking ClCH CON(C H )
3
.13 Synthesis of [Ce(NO
3
)
3
(L
3
)
2
] (11)
2
8
H
17
)
2
, C24
H
41SNO
2
To an absolute ethanol solution of L
solid [Ce(NO ·6H O] (300 mg, 0.691 mmol) was added and
refluxed for 2 h. The resulting white solid was filtered off,
washed with ethanol and dried (yield, 510 mg, 86%). Calc. (%)
3
(400 mg, 1.498 mmol),
1
3
)
2
2
−
1
1
m/cm 1638 (CO), 1047 (SO); H NMR (CDCl
Hz, 6H, CH ), 1.19–1.49 (br m, 24H, CH ), 3.04–3.30 (m, 4H,
NCH ), 3.77 (d, 1H, 14 Hz, SO–CH –CO), 4.06 (d, 1H, 14 Hz,
SO–CH –CO), 7.53–7.57 (m, 3H, Ph), 7. 70 (m, 2H, Ph).
3
): d 0.914 (t,
7
3
2
i
2
2
for [Ce(NO
3
)
3
(PhSOCH
2
CON Pr
2
)
2
], C28
H
42
S
2
N
5
O
13Ce: C 39.1,
2
H 4.9, N 8.1. Found: C 38.4, H 5.1, N 8.0; IR (KBr, Nujol):
−
1
1
m/cm 1592 (CO), 1502, 1378, 1300 (NO
(CD COCD ): d 0.353 (d, 6 Hz, 6H, CH
CH ), 1.236 (d, 6 Hz, 6H, CH ), 1.479 (d, 6 Hz, 6H, CH
.54 (m, 2H, NCH), 4.68 (m, 2H, NCH), 5.85 (d, 13 Hz, 2H,
SO–CH –CO), 6.16 (d, 14 Hz, 2H, SO–CH –CO), 7.97 (m, 6H,
Ph), 8.52 (m, 4H, Ph).
3
), 1014 (SO); H NMR
), 0.874 (d, 6 Hz, 6H,
),
3
.9 Synthesis of [UO
2
(NO
3
)
2
L
1
] (7)
3
3
3
3
3
3
To a solution of [UO
2
(NO
3
)
2
·6H O] in dry acetone (502 mg,
2
3
1
4
.0 mmol), L
1
was added (273 mg, 1.0 mmol) and stirred for
2
2
8 h. The solution on evaporation yielded a pale yellow solid,
which was dissolved in THF (30 mL) and filtered. The filtrate
on evaporation yielded a pale yellow solid, which was filtered
off, washed with chloroform, hexane and dried in an oven at
3
.14 Synthesis of [Ce(NO
3 3 4 2
) (L ) ] (12)
8
(
6
3
0 °C overnight (yield: 635 mg, 95%). Calc. (%) for [UO
PhCH SOCH CONHPh)], C15 10U: C 27.0, H 2.2, N
.3. Found: C 26.8, H 2.4, N 6.1; IR (KBr, Nujol mull): m/cm
2
(NO
3
)
2
-
To an absolute ethanol solution of L (500 mg, 1.69 mmol),
4
2
2
H
15SN
3
O
solid [Ce(NO ·6H O] (300 mg, 0.691 mmol) was added and
3
)
2
2
−
1
refluxed for 2 h. The resulting white solid was filtered off,
washed with ethanol and dried (yield, 580 mg, 92%). Calc. (%)
1
346 (NH), 1630 (CO), 990 (SO), 943 (OUO) ; H NMR
COCD ): d 4.416 (SO–CH –CO), 4.554 (SO–CH –CO),
–SO–), 4.948 (–CH –SO–), 7.21–8. 00 (Ph),
(
CD
3
3
2
2
for [Ce(NO
3 3 2 2 2 50 2 5
) (PhSOCH CONBu ) ], C32H S N O13Ce: C 42.0,
4
1
.838 (–CH
0.45 (NH).
2
2
H 5.5, N 7.7, Found: C 41.5, H 5.7, N 7.8; IR (KBr, Nujol):
−
1
1
m/cm 1595 (CO), 1500, 1378, 1302 (NO ), 990 (SO); H NMR
3
CD COCD ): d 0.75 (t, 7 Hz, 6H, CH ), 1.02 (m, 7 Hz, 4H,
3
(
3
3
3
.10 Synthesis of [UO
2
(NO
3
)
2
L
3
] (8)
CH ), 1.11 (t, 6 Hz, 6H, CH ), 1.26 (m, 6 Hz, 4H, CH ), 1.56
2
3
2
(
m, 7 Hz, 4H, CH
2
), 1.75 (m, 7 Hz, 4H, CH
2
), 3.19 (m, 2H,
To an absolute ethanol solution of L
3
(534 mg, 2.0 mmol)
NCH
SO–CH
2
), 3.44 (m, 2H, NCH
2 2
), 3.71 (m, 4H, NCH ), 5.7 (br, 4H,
solid [UO (NO ·6H O] (502 mg, 1.0 mmol) was added and
2
3
)
2
2
2
–CO), 7.91 (m, 6H, Ph), 8.31 (m, 4H, Ph).
stirred for 5 h. The solvent was evaporated under vacuum
and the residue was extracted with chloroform and filtered.
The chloroform solution on standing overnight deposited a
yellow product, which was filtered off, washed with chloroform
3
.15 Synthesis of [Ce(NO
3 3 5 2
) (L ) ] (13)
To an absolute ethanol solution of L
5
(500 mg, 1.69 mmol),
and dried. It was recrystallized from hot CH
2
Cl
2
–hexane as
solid [Ce(NO ·6H O] (300 mg, 0.691 mmol) was added and
3
)
2
2
a yellow crystalline solid (yield, 600 mg, 91%). Calc. (%) for
refluxed for 2 h. The resulting white solid was filtered off,
i
[
3
1
UO
2
(NO
3
)
2
(PhSOCH
2
CON Pr
2
)], C14
H
21SN
3
O
10U: C 25.4, H
washed with ethanol and dried (yield, 600 mg, 95%). Calc. (%)
−
1
i
.2, N 6.4. Found: C 25.1, H 3.0, N 5.9; IR (KBr, Nujol): m/cm
for [Ce(NO
3
)
2
(PhSOCH
2
CON Bu
2
)], C32
H
50
S
2
N
5
O
13Ce: C 42.0,
1
600 (CO), 978 (SO), 937 (OUO); H NMR (CD
), 1.33 (d, 6 Hz, 3H, CH ), 1.44 (d,
), 1.80 (d, 6 Hz, 3H, CH ), 3.97 (br, 1H, NCH),
.29 (br, 1H, NCH), 4.80 (br, 1H, SO–CH –CO), 5.17 (br, 1H,
–CO), 7.78 (m, 3H, Ph), 8.12 (br d, 2H, Ph).
3 3
COCD ):
H 5.5, N 7.7. Found: C 41.8, H 5.6, N 7.6;. IR (KBr, Nujol):
−
1
1
d 0.98 (d, 6 Hz, 3H, CH
6
4
3
3
m/cm 1600, 1586 (CO), 1498, 1378, 1302 (NO
NMR (CD COCD ): d 0.58 (d, 7 Hz, 6H, CH ), 0.66 (d, 7 Hz,
6H, CH ), 1.38 (d, 6 Hz, 6H, CH ), 1.70 (d, 6 Hz, 6H, CH ),
1.64 (m, 6 Hz, 2H, CH), 1.84 (m, 7 Hz, 1H, CH), 3.49 (m, 4H,
NCH ), 3.53–3.70 (m, 4H, NCH ), 5.40 (br, 2H, SO–CH –CO),
5.66 (br, 2H, SO–CH –CO), 7.90 (m, 6H, Ph), 8.30 (br m,
3
), 990 (SO); H
Hz, 3H, CH
3
3
3
3
3
2
3
3
3
SO–CH
2
2
2
2
3
.11 Synthesis of [UO
2 3 2 4
(NO ) L ] (9)
2
4
H, Ph).
This was prepared similarly to 8 by taking L
4
(580 mg, 2.0 mmol)
and [UO (NO ·6H O] (502 mg, 1.0 mmol). The final product
was recrystallized from hot CH Cl –dodecane as a yellow
powder (yield, 625 mg, 91%). Calc. (%) for [UO (NO (PhSO-
CH CONBu 10U: C 27.9, H 3.6, N 6.1. Found:
C 27.5, H 3.3, N 5.9; IR (KBr, Nujol): m/cm 1602 (CO), 993
2
3
)
2
2
3
.16 X-Ray diffraction studies of 10 and 12
2
2
2
3
)
2
Data for crystals 10 and 12 were measured with Mo-Ka
radiation (k = 0.71073 Å) using the MARresearch Image Plate
System. The crystals were positioned at 70 mm from the Image
Plate. 95 frames were measured at 2° intervals with a count-
ing time of 2 min. Data analysis was carried out with XDS
2
2 3
)], C16H25SN O
−
1
1
(
SO); 938 (OUO); H NMR (CD
3
COCD
3
): d 0.88 (t, 6 Hz,
), 3.57 (br, 2H,
6
H, CH ), 1.31 (m, 4H, CH ), 1.65 (m, 4H, CH
3
2
2
3
6 0 8
D a l t o n T r a n s . , 2 0 0 4 , 3 6 0 4 – 3 6 1 0

View Article Online
Table 3 Crystal and structural refinement details for 10 and 12
12
1981, 16, 403; (f) E. P. Horwitz, D. G. Kalina and A. C. Muscatello,
Sep. Sci. Technol., 1981, 16, 417; (g) W. W. Schulz and J. D. Navratil,
in Recent Developments in Separation Science, ed. N. W. Li, CRC
Press, Boca Raton. FL, 1982, p. 31; (h) E. P. Horwitz, H. Diamond
and D. G. Kalina, in Plutonium Chemistry, ed. W. T. Carnall
and G. R. Choppin, ACS Symposium Series 216, American
Chemical Society, Washington, DC, 1983, p. 179; (i) E. P. Horwitz,
D. G. Kalina, L. Kaplan, G. W. Mason and H. Diamond, Sep.
Sci. Technol., 1982, 17, 1261; (j) E. P. Horwitz, H. Diamond and
A. Martin, Solv. Extr. Ion Exch., 1987, 5, 447; (k) W. W. Schulz and
E. P. Horwitz, Sep. Sci. Technol., 1988, 23, 1191.
(a) C. Musikas, Inorg. Chim. Acta, 1987, 140, 197; (b) C. Cullerdier,
C. Musikas and P. Hoel, in New Separation Technique for Radio-
active Waste and Other Specific Applications, ed. L. Cecille,
M. Cesarci and L. Pietrelli, Elsevier Applied Science, Oxford, 1991,
p. 41; (c) L. Nigond, C. Musikas and C. Cullerdier, Solv. Extr. Ion
Exch., 1994, 12, 297; (d) L. Nigond, C. Musikas and C. Cullerdier,
Solv. Extr. Ion Exch., 1994, 12, 261; (e) L. Nigond, C. Musikas and
C. Cullerdier, Solv. Extr. Ion Exch., 1994, 12, 297; (f) L. Nigond,
N. Condamines, P. Y. Cordier, J. Livert, C. Madic, C. Cullerdier
and C. Musikas, Sep. Sci. Technol., 1995, 30, 2075; (g) C. Madic
and M. J. Hudson, High-level liquid waste partitioning by means of
completely incinerable extractants, European Commission, Nuclear
Science and Technology, EUR18038EN, Luxembourg, 1998.
G. R. Choppin and A. Morgenstern, J. Radioanal. Nucl. Chem.,
1
0
Empirical formula
Formula weight
C
689.5
16
H
25
N
3
O10SU
32 50 5 13 2
C H N O S Ce
916.98
Crystal system
Space group
Triclinic
P1
Monoclinic
C2/c
a/Å
b/Å
c/Å
a/°
9.717(12)
18.825(19)
17.131(19)
16.315(18)
(90)
122.50(1)
(90)
4438(8)
4
1.429
10.139(12)
13.960(15)
96.635(10)
94.068(10)
118.041(10)
1193(2)
2
2
b/°
c/°
V/Å3
Z (formula unit)
/g cm−3
D
c
1.914
Reflections collected/unique
6793/4186
4186/0/284
1.256
8982/3581
3581/6/239
0.783
Data/restraints/parameters
Goodness of fit on F2
Final R indices [I > 2r(I)]
R indices (all data)
0.0635
0.0841
0.1121
0.2278
2
2
2
2
+ 2F 2
w = 1/[r (F ) + (0.0392P) + 6.2832P]; P = (F )/3 for 10 and
o
o
c
2
2
2 2 2
1
o o c
/[r (F ) + (0.100P) ]; P = (F + 2F )/3 for 12.
3
4
2
000, 243, 45.
(a) S. M. Bowen, E. N. Duesler and R. T. Paine, Inorg. Chem.,
982, 21, 261; (b) S. M. Bowen, E. N. Duesler and R. T. Paine,
program.20a The structures were solved using direct methods
1
2
0b
with the SHELX-86 program. In 12 one of the alkyl chains
was disordered with three of the carbon atoms refined over
two sites. Apart from these disordered atoms all non-hydrogen
atoms in both structures were refined with anisotropic thermal
parameters. The hydrogen atoms bonded to carbon atoms
were included in geometric positions and given thermal para-
meters equivalent to 1.2 times those of the atoms to which they
attached. Empirical absorption corrections were carried out
Inorg. Chim. Acta, 1982, 61, 155; (c) S. M. Bowen, E. N. Duesler
and R. T. Paine, Inorg. Chem., 1983, 22, 286; (d) L. J. Caudle,
E. N. Duesler and R. T. Paine, Inorg. Chim. Acta, 1985, 110, 91;
(
e) L. J. Caudle, E. N. Duesler and R. T. Paine, Inorg. Chem.,
985, 24, 4441; (f) D. J. McCabe, A. A. Russell, S. Karthikeyan,
R. T. Paine, R. R. Ryan and B. Smith, Inorg. Chem., 1987, 26, 1230;
g) S. Karthikeyan, R. T. Paine and R. R. Ryan, Inorg. Chim. Acta,
988, 144, 135; (h) S. Karthikeyan, R. R. Ryan and R. T. Paine,
1
(
1
Inorg. Chem., 989, 28, 2783; (i) D. T. Cromer, R. R. Rayan,
S. Karthikeyan and R. T. Paine, Inorg. Chim. Acta, 1990, 172, 165.
2
0c
using the DIFABS program. The structures were refined to
2
20d
5 (a) P. Byers, M. G. B. Drew, M. J. Hudson, N. S. Isaacs and
C. Madic, Polyhedron, 1994, 13, 349; (b) G. Y. S. Chan, M. G. B.
Drew, M. J. Hudson, P. B. Iveson, J. O. Liljenzin, M. Skalberg,
L. Spjuth and C. Madic, J. Chem. Soc., Dalton Trans., 1997,
convergence on F using SHELXL. Selected crystallographic
data for all the compounds are summarized in Table 3.
CCDC reference numbers 238300 and 238301.
See http://www.rsc.org/suppdata/dt/b4/b407824a/ for crystal-
lographic data in CIF or other electronic format.
6
49; (c) P. Thuery, M. Nierlich, M. C. Charbonnel, C. D. Auwer
and J. P. Dognon, Polyhedron, 1999, 18, 3599; (d) P. B. Iveson,
M. G. B. Drew, M. J. Hudson and C. Madic, J. Chem. Soc.,
Dalton Trans., 1999, 3605; (e) B. M. Rapko, B. K. McNamara, R. D.
Rogers, G. J. Lumetta and B. P. Hay, Inorg. Chem., 1999, 38, 4585;
(f) C. D. Auwer, M. C. Charbonnel, M. G. B. Drew, M. Grigoriev,
M. J. Hudson, P. B. Iveson, C. Madic, M. Nierlich, M. T. Presson,
R. Revel, M. L. Russell and P. Thuery, Inorg. Chem., 2000, 39,
4
Conclusion
Studies on the coordinating ability of the carbamoylmethyl
sulfoxide ligand L , L , L and L with uranyl nitrate and
1
3
4
5
cerium(III) nitrate show that the ligands act as bidentate
chelating ligands in all the compounds. These studies suggest
further that the CMSO ligand is a very similar to CMP, CMPO
or malonamides in its coordination behavior. The preliminary
1
487; (g) G. J. Lumetta, B. K. McNamara, B. M. Rapko, R. L. Sell,
R. D. Rogers, G. Broker and J. E. Hutchison, Inorg. Chim. Acta,
000, 309, 103.
2
6
(a) S. R. Mohanthy and A. S. Reddy, J. Inorg. Nucl. Chem., 1975,
37, 1791; (b) A. S. Reddy, V. V. Ramakrishna and S. K. Patil, Radio-
chem. Radioanal. Lett., 1977, 28, 445; (c) S. A. Pai, J. P. Shukla,
P. K. Khopkar and M. S. Subramanian, J. Radioanal. Chem.,
extraction studies of L
level indicate that it extracts U(VI) and Pu(IV) from HNO
6
with U(VI), Pu(IV) and Am(III) at tracer
with
3
concentrations up to 10 M. Am(III) did not show appreciable
extraction under the conditions studied. Electron spray mass
spectra of 8 and 10 in acetone show that extensive ligand
distribution reaction occurs in acetone to give a mixture of
species with ligand to metal ratios of 1:1 and 2:1. TG/DTA
experiments show that the CMSO ligands are easily destroyed
on incineration.
1
978, 42, 323; (d) J. P. Shukla, S. A. Pai and M. S. Subramanian, J.
Radioanal. Chem., 1980, 60, 403; (e) V. Chakravorthy, K. C. Dash
and S. R. Mohanthy, Radiochim. Acta, 1986, 40, 89; (f) Y. Y. Zhao,
S. S. Xiu, Y. Y. Hui and L. H. Bin, J. Radioanal. Nucl. Chem., 2000,
2
46, 263.
7 (a) G. M. Gasparini and G. Grossi, Solv. Extr. Ion Exch., 1986,
4, 1233; (b) C. Musikas, Sep. Sci.Technol., 1988, 23, 1211;
(
1
c) N. Condamines and C. Musikas, Solv. Extr. Ion Exch., 1992,
0, 69.
Acknowledgements
8
9
M. S. Subramanian, J. Radioanal. Nucl. Chem. Lett., 1994, 187, 91.
(a) P. J. Alvey, K. W. Bagnall, O. V. Lopez and D. Brown, J. Chem.
Soc., Dalton Trans., 1975, 1277; (b) U. Casellato, P. A. Vigato and
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0 (a) S. Kannan, M. R. A. Pillai, V. Venugopal, P. A. Droege
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S. Shanmugasundara Raj and H. K. Fun, Acta Crystallogr.,
Sect. C, 2000, 56, e545; (c) S. Kannan, A. Usman, A. Z. Razak,
A. Chandrapromma and H. K. Fun, Acta Crystallogr., Sect. C,
We wish to thank, the Head, Analytical Chemistry Division,
BARC, for carbon and hydrogen analysis and the Head,
National NMR facilities, TIFR, Mumbai for NMR spectra. We
thank the EPSRC (UK) and the University of Reading for funds
for the Image Plate system.
1
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