Four- five and six-co-ordinated pentafluorophenylthallium(III) complexes. Crystal structures of [T1(C6F5)3 (OPPh3)],

Article abstract of DOI:10.1016/S0022-328X(02)01961-7

[NBu₄][Ag(C₆F₅)₂] or [Ag(C₆F₅)] act as arylating ligands able to transfer two or one pentafluorophenyl groups to [Tl(C₆F ₅)₂Cl] leading to [NBu₄][Tl (C₆F₅)₄] (1) and [Tl(C₆F₅)3(diox)] (diox = 1,4 dioxane) (2) in an improved synthesis, the latter being a starting material for the synthesis of [Tl(C₆F₅)₃ (OPPh₃)] (₃) and [Tl(C₆F₅)₃(PPh₃)] (4). However, [Ag(C₆F₅)L] does not transfer the pentafluorophenyl group when reacted with [Tl(C₆F₅) ₂Cl] and the complexes [Tl(C₆F₅) ₂Cl(py)]₂ (5), [Tl(C₆F₅) ₂Cl(OPPh₃)]₂ (6) and [Tl (C₆F₅)₂(OdppmO)₂][Tl (C₆F₅)₂Cl₀2] (7) are obtained as the main products, which can be obtained in a better yield by the addition of the neutral ligands to [Tl(C₆F₅)₂Cl]. The X-ray structure of complexes 3,6 and 7 show thallium(III) centres in a tetrahedral, trigonal bipyramidal or octahedral arrangements, respectively.

Full text of DOI:10.1016/S0022-328X(02)01961-7

Journal of Organometallic Chemistry 663 (2002) 289ꢂ296
/
www.elsevier.com/locate/jorganchem
Four- five- and six-co-ordinated pentafluorophenylthallium(III)
complexes.
Crystal structures of [Tl(C6F5)3(OPPh3)], [Tl(C6F5)2Cl(OPPh3)]2 and
[Tl(C6F5)2(OdppmO)2][Tl(C6F5)2Cl2]
Aranzazu Mendia a,ꢀ, Elena Cerrada b, Eduardo J. Fernandez c, Antonio Laguna b,
Mariano Laguna b,ꢀ
Departamento de Quımica, Universidad de Burgos, Plaza Misael Banuelos, E-09001 Burgos, Spain
a
´
˜
Departamento de Quımica Inorganica, Instituto de Ciencia de Materiales de Aragon, Facultad de Ciencias, Universidad de Zaragoza-C.S.I.C., E-50009
Zaragoza, Spain
b
´
´
´
c
´
Departamento de Quımica, Universidad de la Rioja, E-26004 Logrono, Spain
˜
Received 31 July 2002; received in revised form 17 September 2002; accepted 25 September 2002
Abstract
[NBu4][Ag(C6F5)2] or [Ag(C6F5)] act as arylating ligands able to transfer two or one pentafluorophenyl groups to [Tl(C6F5)2Cl]
leading to [NBu4][Tl(C6F5)4] (1) and [Tl(C6F5)3(diox)] (dioxꢁ1,4 dioxane) (2) in an improved synthesis, the latter being a starting
/
material for the synthesis of [Tl(C6F5)3(OPPh3)] (3) and [Tl(C6F5)3(PPh3)] (4). However, [Ag(C6F5)L] does not transfer the
pentafluorophenyl group when reacted with [Tl(C6F5)2Cl] and the complexes [Tl(C6F5)2Cl(py)]2 (5), [Tl(C6F5)2Cl(OPPh3)]2 (6) and
[Tl(C6F5)2(OdppmO)2][Tl(C6F5)2Cl2] (7) are obtained as the main products, which can be obtained in a better yield by the addition
of the neutral ligands to [Tl(C6F5)2Cl]. The X-ray structure of complexes 3, 6 and 7 show thallium(III) centres in a tetrahedral,
trigonal bipyramidal or octahedral arrangements, respectively.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Thallium; Silver; Aryl transfer; Phosphine oxide; Pentafluorophenyl complexes; Crystal structures
1. Introduction
different structures for complexes with very similar
stoichiometries, mainly due to interactions in solid state.
This is both the source of beautiful structures and the
reason behind a behaviour which is not easy to predict.
Environmental concern has led to studies on the toxicity
of thallium. These have led to the discovery of natural
methylation resulting in TlMe2 derivatives which have
been detected in the oceans [14,15]. This has under-
scored the importance of the studies on dimethyl-
The organometallic chemistry of thallium is of current
interest because of its versatility in structural behaviour
[1ꢂ
/
6], because of its many metalꢂ
/
metal interactions with
13] and because of its
itself or with transition metals [7ꢂ
/
relevance in environmental chemistry [14,15]. Thus,
organometallic thallium complexes with the metal in
different oxidation states such as I, II and III are known;
oxidation state II being the least represented. It is
noteworthy that the reported X-ray structures of
thallium complexes reveal that this element presents
thallium(III) [16ꢂ
(III) derivatives which are poorly represented [1ꢂ
21].
Continuing with our interest in both arylꢂ
chemistry and in the use of arylꢂsilver complexes as
arylating agents [9,22ꢂ29], we report here the use of
/18] complexes and on aryl thallium-
/
4,19ꢂ
/
/
thallium
/
/
ꢀ Corresponding authors. Tel.: ꢃ
/
34-976-771181; fax: ꢃ34-976-
/
[NBu4][Ag(C6F5)2] and [Ag(C6F5)] as arylating agents
capable of transferring one or two pentafluorophenyl
groups to [Tl(C6F5)2Cl]. This leads to a substantial
771187
E-mail addresses: amendia@ubu.es (A. Mendia), mlaguna@
posta.unizar.es (M. Laguna).
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 1 9 6 1 - 7

290
A. Mendia et al. / Journal of Organometallic Chemistry 663 (2002) 289ꢂ296
/
improvement of the synthesis of [NBu4][Tl(C6F5)4] (1)
and [Tl(C6F5)3(diox)] (dioxꢁ1,4-dioxane) (2) compared
to the previously described method using the lithium
derivative LiC6F5 [23] or HBF4 [21]. Complex 2 is a
precursor for the synthesis of [Tl(C6F5)3(OPPh3)] (3)
and [Tl(C6F5)3(PPh3)] (4). However, [Ag(C6F5)L] does
not behave as an arylating agent when reacted with
nylsilver(I) complexes as arylating agents are confirmed,
as we have reported in previous papers [25,28]. Further-
more, this is one of the rare examples in which two C6F5
groups are transferred between two metals. It is
noteworthy that another complex able to transfer two
C6F5 groups is the starting material [Tl(C6F5)2Cl].
This result was determinant in the search for a similar
reaction that would synthesise [Tl(C6F5)3(diox)] (2) from
[Tl(C6F5)2Cl] whilst avoiding the use of excess corrosive
HBF4 [21], required in the previous preparation of 2.
Thus, the reaction between [Tl(C6F5)2Cl] and [Ag(C6F5)]
/
[Tl(C6F5)2Cl] and only [Tl(C6F5)2Cl(L)]2 Lꢁpy (5);
/
OPPh3 (6) and OdppmO (bis(diphenylphosphinemetha-
ne)dioxide) (7) are obtained as the main products of a
complicated mixture. Complexes 5ꢂ7 can be obtained in
/
a pure form by the reaction of [Tl(C6F5)2Cl] with the
appropriate ligand. The lack of many structures in aryl
was carried out in a thalliumꢂsilver 1:1 molar ratio
/
(Scheme 1, Eq. (ii)). The AgCl was filtered off and,
adding dioxane, we managed to isolate a solid from the
solution whose properties correspond to [Tl(C6F5)3-
(diox)] (2) with a yield of 91%.
thallium(III) chemistry*
been totally characterised*
/
no [TlR3(L)] (Rꢁ
/
aryl) has
and the above mentioned
/
versatility of the thallium(III) centre forced us to resolve
the structures of complexes [Tl(C6F5)3(OPPh3)] (3),
[Tl(C6F5)2Cl(OPPh3)]2 (6) and [Tl(C6F5)2(OdppmO)2]-
[Tl(C6F5)2Cl2] (7), which show thallium(III) centres in
such different surroundings as tetrahedral, trigonal
bipyramidal or octahedral arrangements, respectively.
The 19F-NMR spectra of 1 and 2 show the equiva-
lence of pentafluorophenyl groups in each complex,
which is consistent with the tetrahedral co-ordination of
the thallium(III) centre proposed for these complexes. It
is interesting to note that the presence of two active
nuclei 203Tl and 205Tl (29.5 and 70.5% isotopic abun-
dance) with similar gyromagnetic constants made the
signals corresponding to Fo, Fp and Fm atoms appear as
doublets of multiplets, because of the additional cou-
2. Results and discussion
pling between them. These 203,205Tlꢂ
F coupling con-
/
The reaction of [Tl(C6F5)2Cl] with [NBu4][Ag(C6F5)2]
in diethyl ether under inert atmosphere and in 1:1 molar
ratio leads to [NBu4][Tl(C6F5)4] (1), with a very high
yield, 93%, as an air-stable solid at room temperature
whose properties coincide with those previously de-
scribed for this complex [23,27] (Scheme 1, Eq. (i)).
Previous procedures, such as the use of TlCl3 [23] or
[Tl(C6F5)2Br] [27], require an excess of LiC6F5 (6:1 or
4:1 molar ratio, respectively) to get the tetrakis(penta-
fluorophenyl)thallium(III) derivative and produce yields
of only 60 or 54%, respectively, probably due to co-
lateral reactions that take place because of the excess of
lithium reagent. The good properties of polyhalophe-
stants should be different depending on the co-
ordination, as was observed in [Tl(2,4,6-C6F3H2)2]-
[Tl(2,4,6-C6F3H2)Cl3] (i.e.
J
ꢁ
/
880.4 and
187.7 and
298.6 Hz in H-NMR) or in the 203,205Tlꢂ
constants in [Tl(2,4,6-Me3C6H2)2][Tl(2,4,6-
Me3C6H2)Cl3] (i.e. J 168.0 and J ?ꢁ
203;205TlꢄFo/
J
J
?ꢁ
/
913.1 Hz), (i.e.
J
/
ꢁ
/
203;205TlꢄFo/
203;205TlꢄHm
1
/
ꢁ
/
/
203;205TlꢄHm?
H
/
ꢁ
/
/
/
203;205TlꢄHm
203;205TlꢄHm
1
403.9 Hz in the H-NMR) [26]. In these cases, based
on the integration ratios, the largest constants corre-
spond to the aromatic groups in a tetrahedral fashion
and this information agrees with the solid state for the
mesityl complex [25].
[TlR3(diox)] complexes have been used as useful
starting materials for the synthesis of new [TlR3L]
complexes, (Rꢁ
/
2,4,6-C6F3H2 and Lꢁ
/
dppm, OPPh3,
PPh3) [21] or (Rꢁ
/
C6F5 and Lꢁdppm, OdppmO) [22]
/
and so [Tl(C6F5)3(diox)] (2) reacts with OPPh3 or PPh3
leading to the new species [Tl(C6F5)3(OPPh3)] (3) or
[Tl(C6F5)3(PPh3)] (4) (Scheme 1, Eq. (iii)).
Complexes 3 and 4 are non-conducting in acetone
solutions and the IR spectra show absorptions due to
the C6F5-X-sensitive mode at 961 (vs) (3), 962 (vs) (4)
cmꢄ1 and to the phosphine oxide n (OÄ
/
P) 1160 (vs) (3)
cmꢄ1. The last wave number suggests the co-ordination
of the OPPh3 ligand because of the low energy
displacement of n (OÄ
/
P) Dꢁ
33 cmꢄ1 [30]. The 19F-
/
NMR spectra at room temperature in CDCl3 of com-
plexes 3 and 4 show the characteristic pattern, doublet
of multiplets, doublet of triplets and doublet of multi-
plets, due to Fo, Fp and Fm atoms in C6F5 equivalent
Scheme 1.

A. Mendia et al. / Journal of Organometallic Chemistry 663 (2002) 289ꢂ
/296
291
groups. The field displacement of signals and the
coupling 203,205Tlꢂ
F constants are similar for both
complexes. The values of these constants are close to
those found in [NBu4][Tl(C6F5)4] (1) and
Table 1
˚
Bond lengths (A) and angles (8) for [Tl(C6F5)3(OPPh3)] (3)
/
Bond lengths
Tl(1)ÃC(1)
Tl(1)ÃC(13)
2.180(4)
2.190(4)
Tl(1)ÃC(7)
Tl(1)ÃO(1)
2.192(4)
2.300(3)
[Tl(C6F5)3(diox)] (2) suggesting a similar structure for
all these complexes in solution. The room temperature
31P{1H}-NMR spectra show a singlet at 35.60 and 10.55
ppm for 3 and 4, respectively. Cooling the solutions to
Bond angles
C(1)ÃTl(1)ÃC(13)
C(1)ÃTl(1)ÃC(7)
C(13)ÃTl(1)ÃC(7)
C(1)ÃTl(1)ÃO(1)
C(13)ÃTl(1)ÃO(1)
C(7)ÃTl(1)ÃO(1)
P(1)ÃO(1)ÃTl(1)
116.86(14) C(2)ÃC(1)ÃTl(1)
118.51(15) C(6)ÃC(1)ÃTl(1)
122.24(14) C(8)ÃC(7)ÃTl(1)
98.16(13) C(12)ÃC(7)ÃTl(1)
96.86(11) C(18)ÃC(13)ÃTl(1)
90.57(11) C(14)ÃC(13)ÃTl(1)
154.67(16)
121.4(3)
122.9(3)
122.9(3)
120.0(3)
122.0(3)
122.2(3)
ꢄ
/
60 8C in (3) and ꢄ
the splitting of the signal in a doublet of multiplets in
both cases with J203;205TlꢄP ꢁ444.7 (3) and 282.0 (4) Hz.
/
50 8C in (4) allows us to observe
/
/
These values are similar to those found in the few
examples which have been described of [TlR3L] stoi-
chiometry, LꢁCH2PR? [29], where monomer species
are assumed, although none of them have been char-
acterised by X-ray diffraction.
3
[20] and similar to that present in [(C6F5)2TlO2CC6-
F5(OPPh3)]2 [19]. In our case this large angle can be
attributed to steric factors. The TlÃ
/
O bond length of
is comparable to that found in
Since no structures of [TlR3L] complexes are known,
the molecular structure of the complex [Tl(C6F5)3-
(OPPh3)] (3) has been established by X-ray diffraction.
Single crystals were obtained by slow diffusion of
hexane into a concentrated dichloromethane solution
of 3 at room temperature. The mononuclear species is
shown in Fig. 1 and selected bond lengths and angles are
given in Table 1.
˚
A
2.300(3)
[(C6F5)2TlO2CC6F5(OPPh3)]2 [19] (2.391(9) A).
˚
The tetrahedral structure of 3 in the solid state is
compatible with the NMR data in solution and, by
extension, the spectroscopic data suggest that com-
pounds 1ꢂ
solid state.
Attempts to use [Ag(C6F5)L], (Lꢁ
[Ag(C6F5)]ꢃL? (L?ꢁOPPh3 or OdppmO) as arylating
/4 can be tetrahedral both in solution and in
/py), or mixtures of
The molecule of [Tl(C6F5)3(OPPh3)] (3) displays a
distorted tetrahedral arrangement for the thallium
/
/
agents of [Tl(C6F5)2Cl], capable of transferring one
C6F5 group as well as the ligand L or L?, failed and,
instead of the expected [Tl(C6F5)3L] complexes, different
mixtures were obtained in which complexes of the type
[Tl(C6F5)2ClL]2 seem to be present as the main reaction
products (Scheme 1, Eqs. (iv and v)). In order to confirm
this point we have obtained these [Tl(C6F5)2ClL]2
centre with angles ranging from 122.23(14)8 (C(13)Ã
/
Tl(1)Ã
/
C(7)) to 90.59(12)8 (O(1)Ã
/
Tl(1)Ã
/
C(13)). The TlÃ
/
˚
C bond distances of 2.179(4), 2.190(4) and 2.193(4) A
are comparable to those found in [Tl{CH2COMe}2(m-
CF3SO3)(bipy)]2 [31] (2.16(8) and 2.171(7) A) and
˚
[Tl(C6F5)2Cl{Au(C6F5)3(PPh2PCH2PPh2(O))}2]
˚
[32]
P(1) angle is
(2.18(2) A). Although the Tl(1)Ã
/
O(1)Ã
/
complexes (Lꢁ
through the reaction of [Tl(C6F5)2Cl] with Lꢁ
/
py (5); OPPh3 (6); OdppmO (7))
py,
very large [154.68(17)8] it is smaller than the correspond-
ing angle (168.08) of [Tl(2,3,5,6-C6F4H)2Cl(OPPh3)]2
/
OPPh3 or OdppmO, leading to complexes 5, 6 and 7
with good yields as a result of the addition of the neutral
ligand to the starting material (Scheme 1, Eq. (vi)).
The IR spectra show absorptions from the penta-
fluorophenyl group and no difference is observed in the
C6F5-X-sensitive mode, 964 (vs) (5) 965 (vs) (6) and 962
(vs) (7) cmꢄ1. The n (OÄ
/
P) is assumed at 1171 (vs, br)
Cl)
(6) and 1184 (vs) cmꢄ1 (7) [30], and the two (TlÃ
/
bands at 226 (s), 260 (m) cmꢄ1 in (7) change into a
single band at 258 (m) cmꢄ1 in (5) and 246 (m) cmꢄ1 in
(6). Although it was proposed [33] that when (TlÃ
/
Cl)
appears below 300 cmꢄ1 it is associated to polymer or
dimer systems with halogen bridging, there are some
examples of terminal (TlÃ/Cl) bands below this value,
such as in [Tl(2,4,6-Me3C6H2)2][Tl(2,4,6-Me3C6H2)Cl3]
[25]. The acetone solutions of complexes 5 and 6 show
no electrolyte behaviour while that of 7 leads to lower
values than those characteristic in 1:1 electrolytes [34].
1
The H-NMR spectra at room temperature of com-
plexes 5ꢂ
/
7 show the assignable resonances to the ligands
Fig. 1. View of the molecular structure of 3 (ellipsoids are drawn at
50% probability level). H atoms have been omitted for clarity.
in the aromatic region. In addition, complex 7 shows a

292
A. Mendia et al. / Journal of Organometallic Chemistry 663 (2002) 289ꢂ296
/
triplet at 3.59 ppm for two equivalent methylene protons
13.4 Hz, which agrees with a symmetrical
lengths are in the range of those found in complex 3. The
˚
Cl distance (2.9498(12) A) is similar to those
with a JPÃH
ꢁ
/
longer TlÃ
/
arrangement of the ligand. The 31P{1H}-NMR spectra
at room temperature in CDCl3 of complexes 6 and 7
show a singlet at 36.62 and 30.3 ppm, respectively.
Lower temperatures do not provide a better resolution
found in thallium complexes with bridging chlorine
˚
atoms, such as [Tl2(CH2SiMe3)4(m-Cl)2] (2.993(3) A)
˚
[35], [Tl2(C,NÃ
/
C6H4CH2NMe2)2Cl2(m-Cl)2] (2.936(3) A)
˚
[36] and (Pip)2[Tl2Cl8(m-Cl)2] (2.893(4) A) [37] and to the
longer TlÃCl distance in [Tl(C6F4H)2Cl(OPPh3)]2
Cl distance
(2.5339(13) A) is similar to those found in terminal
to understand the 203,205Tlꢂ
/P coupling constants system
/
˚
and only in the former case is it possible to recognise a
broadening in the signal that splits into a multiplet,
centred at 32.90 ppm, when a (CD3)2CO solution is used
(2.936(3) A) [20]. The shorter TlÃ
/
˚
choride atoms (see below), including those in complex 7
and the experiment is recorded at ꢄ
/
80 8C. On the other
7 show the signals
and to the shorter TlÃ
Cl(OPPh3)]2 (2.541(3) A) [20]. The main distortion
from regular trigonal bipyramidal geometry is repre-
/
Cl distance in [Tl(C6F4H)2-
hand, the 19F-NMR spectra of 5ꢂ
/
˚
corresponding to only one equivalent pentafluorophenyl
group, which remains even if the temperature is lowered
sented by the CÃ
/
TlÃ
/
C 139.41(17)8 angle. The very large
to ꢄ
Fo, Fp and Fm of the same order of magnitude in all
these complexes, although smaller than in complexes 1ꢂ
/
80 8C, with 203,205Tlꢂ
/F coupling constants for the
value for the PÃOÃ
/
/
Tl 164.1(2)8 angle is similar (168.08)
to that found in [Tl(C6F4H)2Cl(OPPh3)]2 [20], where the
large value was not attributed to any intramolecular
steric factors but was rather based on the easy deforma-
/
4. With all these data it is not easy to propose the
structure of these complexes. This is because the
molecular structures of complexes [Tl(C6F5)2Cl-
(OPPh3)]2 (6) and [Tl(C6F5)2(OdppmO)2][Tl(C6F5)2Cl2]
(7) have been established by X-ray diffraction (Figs. 2
and 3) on single suitable crystals obtained by slow
tion of MÃ
/
OÃ/P angles that could be affected by crystal
packing factors. Fig. 2 shows how pentafluorophenyl
groups are contributing to this effect.
[Tl(C6F5)2(OdppmO)2][TlCl2(C6F5)2] (7) crystallises
¯
in the P1 space group with both cation and anion being
thallium complexes. The anion [Tl(C6F5)2Cl2] displays a
distorted tetrahedral geometry where the main distor-
diffusion from dichloromethaneꢂdiethyl ether. Selected
/
bond lengths and angles are given in Tables 2 and 3.
The molecular structure of complex 6, which exhibits
a crystallographic centre of symmetry, comprises two
distorted trigonal pyramidal Tl(C6F5)2Cl(OPPh3) units
tion comes from the C(11)Ã
135.8(3)8. The TlÃC bond distances (2.167(7) and
2.177(7) A) are similar to those found in complex 3
/
Tl(1)Ã
/
C(21) angle of
/
˚
˚
linked through two different TlÃ
/
Cl bridging bonds. The
and the TlÃ
are in the range of the TlÃ
complexes such as [TlClBrI(OPPh3)2] (2.469(1) A) [38]
/
Cl bond lengths (2.4968(19) and 2.567(2) A)
apical positions are occupied by the two pentaflurophe-
nyl rings giving an angle of 139.41(17)8. Two of these
rings are close to perpendicular to each other, with a
dihedral angle of about 7.68. The OPPh3 and the two
/
Cl terminal distances in
˚
˚
C5H5N (2.520(6) and 2.498(4) A)
and [TlCl3(C5H5N)3]×
/
[39]. The co-ordination around the thallium in the
cation [Tl(C6F5)2(OdppmO)2] can be rationalised as
derived from a distorted octahedron with the penta-
bridging chlorines occupy the equatorial sites. The TlÃ
/O
˚
˚
C (2.168(5) and 2.156(4) A) bond
(2.380(3) A) and TlÃ
/
Fig. 2. Solid state molecular structure of 6. Displacement ellipsoids drawn at the 50% probability level. H atoms are omitted for clarity.

A. Mendia et al. / Journal of Organometallic Chemistry 663 (2002) 289ꢂ
/296
293
Fig. 3. Solid state structure of 7 showing the cation and the anion. Displacement ellipsoids drawn at the 50% probability level. H atoms are omitted
for clarity.
Table 2
Table 3
˚
˚
Bond lengths (A) and angles (8) for [Tl2(C6F5)4(m-Cl)2(OPPh3)2] (6)
Bond lengths (A) and angles (8) for [Tl(C6F5)2(OdppmO)2]-
[TlCl2(C6F5)2] (7)
Bond lengths
Tl(1)ÃC(1)
Tl(1)ÃC(7)
Tl(1)ÃO(1)
Tl(1)ÃCl(1)
2.156(4)
2.168(5)
2.380(3)
2.5339(13)
Tl(1)ÃCl(1)#1
Cl(1)ÃTl(1)#1
O(1)ÃP(1)
2.9498(12)
2.9498(12)
1.496(3)
Bond lengths
Tl(1)ÃC(11)
Tl(1)ÃC(21)
Tl(1)ÃCl(1)
Tl(1)ÃCl(2)
Tl(2)ÃC(31)
Tl(2)ÃC(41)
Tl(2)ÃO(1)
Tl(2)ÃO(4)
2.167(7)
2.177(7)
Tl(2)ÃO(3)
Tl(2)ÃO(2)
2.559(4)
2.689(4)
1.496(4)
1.491(4)
1.498(4)
1.486(4)
2.4968(19) P(1)ÃO(1)
2.567(2)
2.111(6)
2.121(6)
2.393(4)
2.406(4)
P(2)ÃO(2)
P(3)ÃO(4)
P(4)ÃO(3)
Bond angles
C(1)ÃTl(1)ÃC(7)
C(1)ÃTl(1)ÃO(1)
C(7)ÃTl(1)ÃO(1)
C(1)ÃTl(1)ÃCl(1)
C(7)ÃTl(1)ÃCl(1)
O(1)ÃTl(1)ÃCl(1)
C(1)ÃTl(1)ÃCl(1)#1
C(7)ÃTl(1)ÃCl(1)#1
139.41(17) O(1)ÃTl(1)ÃCl(1)#1 169.19(9)
91.32(15) Cl(1)ÃTl(1)ÃCl(1)# 181.08(5)
89.39(14) Tl(1)ÃCl(1)ÃTl(1)#
111.44(13) P(1)ÃO(1)ÃTl(1)
109.15(12) C(2)ÃC(1)ÃTl(1)
88.90(9) C(6)ÃC(1)ÃTl(1)
96.09(12) C(8)ÃC(7)ÃTl(1)
90.08(11) C(12)ÃC(7)ÃTl(1)
194.10(4)
164.1(2)
125.3(3)
117.2(4)
123.9(4)
119.3(3)
Bond angles
C(11)ÃTl(1)ÃC(21) 135.8(3)
O(4)ÃTl(2)ÃO(3)
76.50(13)
86.78(18)
82.78(19)
72.96(13)
150.51(13)
132.95(12)
138.5(2)
C(11)ÃTl(1)ÃCl(1)
C(21)ÃTl(1)ÃCl(1)
C(11)ÃTl(1)ÃCl(2)
C(21)ÃTl(1)ÃCl(2)
Cl(1)ÃTl(1)ÃCl(2)
107.67(18) C(31)ÃTl(2)ÃO(2)
106.46(17) C(41)ÃTl(2)Ã0(2)
100.06(19) O(1)ÃTl(2)ÃO(2)
99.55(19) O(4)ÃTl(2)ÃO(2)
101.80(8)
O(3)ÃTl(2)ÃO(2)
P(1)ÃO(1)ÃTl(2)
C(31)ÃTl(2)ÃC(41) 158.1(2)
flourophenyl groups occupying the trans positions
(C(41)ÃTl(2)ÃC(41)ꢁ158.1(2)8). The two bis(diphenyl-
phosphinemethane)dioxide molecules occupy the equa-
torial positions with OÃTlÃOcis angles ranging from
72.96(13) to 132.95(12)8 and OÃTlÃOtrans with values of
153.64(13) and 150.51(13)8. The TlÃC bond distances of
2.111(6) and 2.121(6) A are shorter than the correspond-
ing distances found in the anion. Two of the four TlÃ
C(31)ÃTl(2)ÃO(1)
C(41)ÃTl(2)ÃO(1)
C(31)ÃTl(2)ÃO(4)
C(41)ÃTl(2)ÃO(4)
O(1)ÃTl(2)ÃO(4)
C(31)ÃTl(2)ÃO(3)
C(41)ÃTl(2)ÃO(3)
O(1)ÃTl(2)ÃO(3)
98.47(19) P(2)ÃO(2)ÃTl(2)
96.76(19) P(4)ÃO(3)ÃTl(2)
93.16(19) P(3)ÃO(4)ÃTl(2)
133.1(2)
136.4(2)
141.3(2)
/
/
/
105.3(2)
C(12)ÃC(11)ÃTl(1) 125.0(5)
/
/
77.90(14) C(16)ÃC(11)ÃTl(1) 120.3(5)
89.15(18) C(22)ÃC(21)ÃTl(1) 121.3(6)
84.07(18) C(26)ÃC(21)ÃTl(1) 122.7(6)
153.64(13) C(36)ÃC(31)ÃTl(2) 119.4(5)
/
/
/
˚
/O
˚
bond lengths (2.393(4) and 2.406(4) A) are slightly
longer than those observed in complex 3. However,
the two remaining bond lengths are remarkably longer
and 6 should have dimer structures even in solution,
because the data are compatible with this possibility
and, in the case of 7, some interchangeable equilibrium
˚
(2.559(4) and 2.689(4) A).
The structures of complexes 6 and 7 do not fit in
perfectly with the solution data, mainly NMR, in which
between the dimer and cationꢂ
solution. The preparation of complexes 5ꢂ
form allows us to confirm that these products are
/
anion structures exists in
/7 in a pure
complexes 5ꢂ7 show similar behaviour. Complexes 5
/

294
A. Mendia et al. / Journal of Organometallic Chemistry 663 (2002) 289ꢂ296
/
present in the reaction mixtures of [Ag(C6F5)L] with
[Tl(C6F5)2Cl] (see above) although other pentafluoro-
phenylthallium(III) complexes are present.
1635 (vs); (NBu4)ꢁ
/
884 (s). 19F-NMR ((CD3)2CO): d
419.9 Hz), ꢄ157.79 (dt, JTlꢂF
o19.3 Hz), ꢄ162.41 (dm, JTlꢂF p ꢁ
ꢄ
/
115.95 (dd, JTlꢂF
ꢁ
/
/
ꢁ
/
51.3 Hz, JF ꢂF
/
ꢁ
/
/
/
p
m
m
To conclude, we have described an improved synth-
esis of [NBu4][Tl(C6F5)4] and [Tl(C6F5)3(diox)] proving
the excellent behaviour of [NBu4][Ag(C6F5)2] and
[Ag(C6F5)] as arylating ligands, the former being able
to transfer even two C6F5 groups to the same
thallium(III) centre. The [Ag(C6F5)L] complexes failed
to transfer the pentafluorophenyl group and [Tl(C6F5)2-
ClL] complexes were obtained as the main products of
more complicated reactions. The synthesis of these
complexes [Tl(C6F5)2ClL] through the addition of the
appropriate ligand to [Tl(C6F5)2Cl] confirms this point.
The X-ray structure determinations of three complexes
once more show the versatility of the thallium(III) centre
to adopt different co-ordination forms. In our case,
using in all instances phosphine oxide ligands, the
pentafluorophenyl derivatives resulted in tetrahedral
[Tl(C6F5)3(OPPh3)] (3), trigonal bipyramidal [Tl(C6F5)2-
Cl(OPPh3)]2 (6) or octahedral [Tl(C6F5)2(Odpp-
mO)2][Tl(C6F5)2Cl2] (7) co-ordination of thallium(III)
centres and, in the case of 7, in a tetrahedral arrange-
ment of the anion as well.
145.1 Hz).
3.2.2. Synthesis of [Tl(C6F5)3(diox)] (2)
To a solution of [Tl(C6F5)2Cl] (0.203 g, 0.35 mmol) in
hot C6H5CH3 (20 ml) was added [Ag(C6F5)] (0.096 g,
0.35 mmol) and the mixture was stirred in reflux for 5 h
under nitrogen. The AgCl was filtered off and the
solution was carried out to dryness dissolving the solid
residue in Et2O (15 ml). Addition of 1,4-dioxane (5 ml)
and C6H14 (20 ml) gave a white precipitate of
[Tl(C6F5)3(diox)]. Yield (%): 91. Anal. Calc. for
C22H8F15O2Tl: C, 33.30; H, 1.02. Found for 2: C,
33.47; H, 1.15%. IR (cmꢄ1, Nujol): (C6F5)ꢁ
1512, 1635 (vs); (diox)ꢁ
/
957,
862, 894 (vs). 19F-NMR
531.2 Hz), ꢄ153.39
19.3 Hz), ꢄ160.19 (dm,
/
(CDCl3): d ꢄ
(dt, JTlꢂF 57.3 Hz, JF ꢂF
JTlꢂF ꢁ p
187.2 Hz).
/
117.62 (dm, JTlꢂF
ꢁ
/
/
o
ꢁ
/
ꢁ
/
/
/
p
m
/
m
3.2.3. Synthesis of [Tl(C6F5)3(OPPh3)] (3)
To a suspension of [Tl(C6F5)3(diox)] (0.194 g, 0.25
mmol) in CH2Cl2 (20 ml) was added OPPh3 (0.068 g,
0.25 mmol) and the dissolution of the thallium complex
was immediately observed. After 1 h of stirring at r.t. the
solution was concentrated to 5 ml and the addition of
C6H14 (20 ml) led to the precipitation of the new
complex as colourless solid. It was filtered off, washed
with C6H14 and dried in vacuum. Yield (%): 60. Anal.
Calc. for C36H15F15OPTl: C, 43.95; H, 1.55. Found for
3. Experimental
3.1. General procedures
IR spectra were recorded on a Perkinꢂ
spectrophotometer, over the range 4000ꢂ
/
Elmer 883
/
200 cmꢄ1
,
using Nujol mulls between polyethylene sheets. 1H-,
31P- and 19F-NMR spectra were recorded on a Varian
UNITY 200 or 300 or BRUKER 300 in CDCl3 or
(CD3)2CO solutions; chemical shifts are quoted relative
to SiMe4 (1H), H3PO4 (external 31P) and CFCl3
(external,19F). The C, H, N analyses were performed
3: C, 44.6; H, 1.35%. IR (cmꢄ1, Nujol): (C6F5)ꢁ
1504, 1632 (vs); (OPPh3)ꢁ471, 487, 515 (m), 539 (vs),
601 (m), 693 (vs), 743, 753 (s), 780, 1160 (vs), 1592 (m).
/961,
/
LM (Vꢄ1 cm2 molꢄ1): 1. 19F-NMR (CDCl3): d
ꢄ
JTlꢂF
/
118.48 (dm, JTlꢂF
ꢁ
/
551.1 Hz),
19.3 Hz), ꢄ
208.1 Hz). 31P{1H}-NMR (CDCl3); (CDCl3,
444.7 Hz).
ꢄ
/
153.51 (dt,
o
with a PerkinꢂElmer 2400 microanalyser. [Ag(C6F5)]
/
ꢁ
/
57.9 Hz, JF ꢂF ꢁ
/
/160.24 (dm,
/
p
p
m
[40], [NBu4][Ag(C6F5)2] [40], [Tl(C6F5)2Cl] [41] were
prepared by established procedures.
JTlꢂF
ꢁ
/
m
ꢄ
/
60 8C: d 35.60 (s); 36.17 (dm, JTlꢂP
ꢁ
/
3.2. Synthesis
3.2.4. Synthesis of [Tl(C6F5)3(PPh3)] (4)
3.2.1. Synthesis of [NBu4][Tl(C6F5)4] (1)
The same procedure as above was used starting from
[Tl(C6F5)3(diox)] (0.095 g, 0.12 mmol) and PPh3 (0.031
g, 0.12 mmol). Yield (%): 72. Anal. Calc. for
C36H15F15PTl: C, 44.65; H, 1.55. Found for 4: C, 44.2;
To a solution of [Tl(C6F5)2Cl] (0.110 g, 0.19 mmol) in
Et2O (30 ml) was added [NBu4][Ag(C6F5)2] (0.131 g,
0.19 mmol) and the mixture was stirred at room
temperature (r.t.) for 2 h under nitrogen. The insoluble
AgCl was filtered off and the solution was concentrated
in vacuum to 5 ml. The addition of C6H14 (20 ml) led to
the precipitation of the complex as colourless solid,
which was filtered off, washed with C6H14 and dried in
vacuum. Yield (%): 93. Anal. Calc. for C36H15F15OPTl:
C, 43.08; H, 3.25; N, 1.26. Found for 1: C, 43.66; H,
H, 1.15%. IR (cmꢄ1, Nujol): (C6F5)ꢁ
(vs); (PPh3)ꢁ501(s), 521, 694, 747 (vs), 777 (s). LM
(Vꢄ1 cm2 molꢄ1): 10. 19F-NMR (CDCl3): d ꢄ
117.02
(dm, JTlꢂF 536.3 Hz), ꢄ153.48 (dt, JTlꢂF 57.9 Hz,
JF ꢂF 160.24 (dm, JTlꢂF
1o9.3 Hz), ꢄ p 186.1 Hz).
31P{1H)-NMR (CDCl3); d 10.55 (s) (CDCl3, ꢄ
10.66 (dm, JTlꢂP 282.0 Hz).
/
962, 1504, 1634
/
/
ꢁ
/
/
ꢁ
/
ꢁ
/
/
ꢁ
/
/
p
m
m
/
50 8C);
3.42; N, 1.38%. IR (cmꢄ1, Nujol): (C6F5)ꢁ
/
953, 1508,
ꢁ
/

A. Mendia et al. / Journal of Organometallic Chemistry 663 (2002) 289ꢂ
/296
295
3.2.5. Synthesis of [Tl(C6F5)2Cl(py)]2 (5)
0.71073) with a nominal crystal to detector distance of
4.0 cm.
To a solution of [Tl(C6F5)2Cl] (0.143 g, 0.25 mmol) in
Et2O (30 ml) was added pyridine (0.020 g, 0.25 mmol)
and a white precipitate appeared immediately. The
suspension was stirred for 1 h at r.t. and the solid
filtered off, washed with C6H14 and dried in vacuum.
Yield (%): 89. Anal. Calc. for C17H5ClF10NTl: C, 31.3;
H, 0.8; N, 2.15. Found for 5: C, 31.8; H, 0.6; N, 2.25%.
3.3.1. Crystal data and data collection parameters
Compound 3 C36H15F15OPTl, Mꢁ
nic, aꢁ11.770(2), bꢁ12.931(3), cꢁ23.439(5) A, bꢁ
100.34(3)8. Vꢁ3509.5(12) A , Tꢁ293(2) K, space
group P2(1)/n, Zꢁ4, Dcalc
1.862 mg mꢄ3, F(000)ꢁ
1880, colourless prism with dimensions 0.55ꢅ0.4ꢅ0.35
mm, mꢁ
4.757 mmꢄ1, u range for data collection 1.77ꢂ
28.328, 155h 515; 135k 517, 315l 531;
/983.82, monocli-
˚
/
/
/
/
3
˚
/
/
/
ꢁ
/
/
IR (cmꢄ1 Nujol): (C6F5)ꢁ
Cl)ꢁ258 (m); (py)ꢁ694, 754, 1509, 1604 (vs). LM
(Vꢄ1 cm2 molꢄ1): 2. 19F-NMR (CDCl3): d ꢄ
115.0
(dm, JTlꢂF 789.6 Hz), ꢄ147.75 (dt, JTlꢂF 84.6 Hz,
JF ꢂF 155.0 (dm, JTlꢂF 338.4 Hz).
5o6.4 Hz), ꢄ
/
964 (vs), 1635 (vs); (TlÃ
/
/
/
/
/
/
/
/
ꢄ
/
/
/
ꢄ
/
/
/
ꢄ
/
/
/
ꢁ
/
/
ꢁ
/
24 319 reflections collected, 8727 independent (Rint
0.0468).
ꢁ
/
p
ꢁ
/
/
ꢁ
/
/
p
m
m
Compound 6 C30H15ClF10OPTl, Mꢁ
clinic, aꢁ21.803(4), bꢁ15.535(3), cꢁ18.637(4) A, bꢁ
107.82(3)8, Vꢁ 298(2) K, space group
C2/c, Zꢁ8, Dcalc 3248,
1.884 mg mꢄ3, F(000)ꢁ
colourless prism with dimensions 0.45ꢅ0.35ꢅ0.35
mm, mꢁ
5.603 mmꢄ1, u range for data collection
1.64ꢂ28.338, ꢄ275h 529, ꢄ205k 520, ꢄ245l 5
15; 20 549 reflections collected, 7415 independent
(Rint 0.0469).
Compound 7 C74H44Cl2F20O4P4Tl2, Mꢁ
triclinic, aꢁ14.346(5), bꢁ16.239(5), cꢁ16.738(5) A,
aꢁ91.338(5), bꢁ100.34(3), gꢁ93.288(5)8, Vꢁ3720(2)
1.768
1912, colourless prism with dimen-
0.35 mm, mꢁ
4.582 mmꢄ1, u range
for data collection 1.65ꢂ28.388, ꢄ185h 519, ꢄ175
k 521, ꢄ225l 521; 26 705 reflections collected, 18 110
independent (Rint 0.0450).
/
852.21, mono-
˚
/
/
/
/
3.2.6. Synthesis of [Tl(C6F5)2Cl(OPPh3)]2 (6)
3
˚
/
6010(2) A , Tꢁ
/
The same procedure as above was used starting from
[Tl(C6F5)2Cl] (0.125 g, 0.22 mmol) and OPPh3 (0.061 g,
0.22 mmol). Yield (%): 90. Anal. Calc. for
C30H15ClF10OPTl: C, 42.28; H, 1.77. Found for 6: C,
/
ꢁ
/
/
/
/
/
42.23; H, 1.46%. IR (cmꢄ1, Nujol): (C6F5)ꢁ
1636 (vs); (TlÃCl)ꢁ246(s); (OPPh3)ꢁ461 (w), 490, 508
/965, 1512,
/
/
/
/
/
/
/
/
/
/
/
/
/
ꢁ
/
(vw), 540 (vs), 606 (w), 696, 746 (vs), 757, 791(s), 1171
(vs, br), 1590 (m). LM (Vꢄ1 cm2 molꢄ1): 4. 19F-NMR
/1980.61,
˚
/
/
/
(CDCl3): d ꢄ
Hz), ꢄ151.35 (dt, JTlꢂF
Hz), ꢄ
159.58 (dt, JTlꢂFp ꢁ
31P{1H}-NMR (CDCl3):
80 8C: d 32.90 (s, br).
/
119.33 (dd, JTlꢂF
ꢁ
/
829.47 Hz, Jꢁ
/
20.67
19.29
/
ꢁ
/
81o.29 Hz, JF ꢂF
ꢁ
/
/
/
/
/
/
3
p
m
˚
¯
A , Tꢁ
mg mꢄ3, F(000)ꢁ
sions 0.45ꢅ0.35ꢅ
/
298(2) K, space group P1; Zꢁ
/
2, Dcalc
ꢁ
/
/
/
348.6 Hz, Jꢁ
/
17.91 Hz).
36.62 (s); (CD3)2CO,
m
/
d
/
/
/
ꢄ
/
/
/
/
/
/
/
/
/
/
/
3.2.7. Synthesis of
[Tl(C6F5)2(OdppmO)2][Tl(C6F5)2Cl2] (7)
ꢁ
/
The same procedure as above was used starting from
[Tl(C6F5)2Cl] (0.143 g, 0.25 mmol) and OdppmO (0.104
g, 0.25 mmol) Yield (%): 90. Anal. Calc. for
C37H22ClF10O2P2Tl: C, 44.85; H, 2.25. Found for 7:
3.3.2. Structure solution and refinement
The structures were solved by direct methods
(
SHELXS-97) [42] and refined by full-matrix least-squares
on F2, using the program SHELXL-97 [43]. All data were
corrected using the program SADABS [44]. The non-
hydrogen atoms were refined with anisotropic thermal
parameters. All hydrogen atoms were included in
C, 45.05; H, 2.30%. IR (cmꢄ1, Nujol): (C6F5)ꢁ
1509, 1633 (vs); (TlÃCl)ꢁ226(s), 260 (m); (OdppmO)ꢁ
506, 690, 740, 1184 (vs). LM (Vꢄ1 cm2 molꢄ1): 64. H-
NMR (CDCl3): d 3.59 (t, JPÃH 13.4 Hz, 2H, ÃCH2Ã),
7ꢂ 119.10 (dm,
8 (m, 20H, Ph). 19F-NMR (CDCl3): d ꢄ
JTlꢂF 68.9 Hz),
373.4 Hz). 31P{1H}-NMR
/
962,
/
/
/
1
ꢁ
/
/
/
idealised positions. Refinement proceeded to: 3 Rꢁ
0.031, wRꢁ0.0677 for 489 parameters, and Rꢁ0.0544
wRꢁ0.0744 for all data, electron density fluctuates in
the range 0.723 and -1.102 e Aꢄ3. Compound 6 Rꢁ
0.0338, wRꢁ0.0654 for 393 parameters, and Rꢁ0.0646
wRꢁ0.0760 for all data, electron density fluctuates in
the range 1.081 and ꢄ
0.0489, wRꢁ0.0947 for 956 parameters, and Rꢁ
wRꢁ0.1134 for all data, electron density fluctuates in
/
/
/
/
/
ꢁ
/
877.7 Hz), ꢄ
/
152.20 (dm, JTlꢂF
ꢁ
/
/
o
p
ꢄ
/
159.80 (dm,
J
ꢁ
/
TlꢂFm
˚
/
(CDCl3): d 30.30(s).
/
/
/
1.383 e Aꢄ3. Compound 7 Rꢁ
0.1095
/
˚
3.3. Crystal structure determination of compounds 3, 6
and 7
/
/
/
/
ꢄ3
˚
Single crystals were grown by diffusing C6H14 into a
CH2Cl2 solution of complex [Tl(C6F5)3(OPPh3)] (3), or
the range 1.270 and -1.171 e A
.
Et2O into
a
CH2Cl2 solution of complexes
[Tl(C6F5)2Cl(OPPh3)]2 (6) and [Tl(C6F5)2(Odpp-
mO2)][TlCl2(C6F5)2] (7), and mounted in inert oil.
Crystals of 3, 6 and 7 were mounted on a glass fibre
4. Supplementary material
Tables of thermal parameters and observed and
calculated structure factors for compounds 3, 6 and 7
have been deposited at the Cambridge Crystallographic
on a Brukerꢂ
/
Siemens Smart CCD diffractometer using
Ka radiation (lꢁ
graphite monochromated Moꢂ
/
/

296
A. Mendia et al. / Journal of Organometallic Chemistry 663 (2002) 289ꢂ296
/
[18] J.S. Casas, E.E. Castellano, A. Sanchez, J. Sordo, M.J. Vidarte,
Polyhedron 17 (1998) 2249.
Data Centre, CCDC nos. 190932ꢂ34 respectively. Any
/
request for this material should quote a full literature
citation which can be obtained from The Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
[19] K. Henrick, M. McPartlin, G.B. Deacon, R.J. Phillips, J.
Organomet. Chem. 204 (1981) 287.
[20] K. Henrick, M. McPartlin, R.W. Matthews, G.B. Deacon, R.J.
Phillips, J. Organomet. Chem. 193 (1980) 13.
[21] R. Uso´n, A. Laguna, J.A. Abad, E. de Jesu´s, J. Chem. Soc.
Dalton Trans. (1983) 1127.
(Fax:
ac.uk or www: http://www.ccdc.cam.ac.uk).
ꢃ44-1223-336033; e-mail: deposit@ccdc.cam.
/
[22] E.J. Ferna´ndez, P.G. Jones, A. Laguna, A. Mend´ıa, Inorg. Chim.
Acta 215 (1994) 229.
Acknowledgements
[23] R. Uso´n, A. Laguna, J.A. Abad, J. Organomet. Chem. 194 (1980)
265.
The authors wish to thank the University of Burgos
(N049, N069) and the Direccio´n General de Estudios
Superiores (PB98-0542) for their financial support.
[24] R. Uso´n, A. Laguna, T. Cuenca, J. Organomet. Chem. 194 (1980)
271.
[25] A. Laguna, E.J. Fena´dez, A. Mendia, M.E. Ruiz-Romero, P.G.
Jones, J. Organomet. Chem. 365 (1989) 201.
[26] A. Mend´ıa, PhD Tesis, Univerisidad de la Rioja. ISBN-84-88713-
41-X (1997).
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