Platinum-thallium cluster complexes

Article abstract of DOI:10.1039/b107579a

The synthesis of new Pt₃Tl complexes [Pt₃{μ₃-Tl(diketonate)(OH₂)}(μ₃ -CO)(μ-dppm)₃][PF₆]₂, 2, dppm = Ph₂CH₂PPh₂, by reversible addition of thallium(I) β-diketonates to the complex cation [Pt₃(μ₃-CO)(μ-dppm)₃]²⁺, is reported. The thallium(I) units are easily displaced from platinum by halide ions X^- (X = Cl, Br, I) to give [Pt₃(μ₃-CO)(μ₃-X)(μ-dppm)₃] ⁺, or by SnCl₃^- to give [Pt₃(μ₃-CO)(μ₃-SnCl₃)(μ-dpp m)₃]⁺. With trifluoroacetate there was an equilibrium with [Pt₃(μ₃-CO)(μ₃-O₂CCF₃ )(μ-dppm)₃]⁺ and [Pt₃{μ₃-Tl(diketonate)(O₂CCF₃)}( μ₃-CO)-(μ-dppm)₃]⁺. The structures of two Pt₃Tl clusters are reported, and the Pt₃Tl unit is shown to be tetrahedral.

Full text of DOI:10.1039/b107579a

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Platinum–thallium cluster complexes
Raisa Stadnichenko, Brian T. Sterenberg, Arlene M. Bradford, Michael C. Jennings
and Richard J. Puddephatt*
Department of Chemistry, University of Western Ontario, London, N6A 5B7, Canada
Received 21st August 2001, Accepted 3rd December 2001
First published as an Advance Article on the web 13th February 2002
The synthesis of new Pt3Tl complexes [Pt3{µ3-Tl(diketonate)(OH2)}(µ3-CO)(µ-dppm)3][PF6]2, 2, dppm =
Ph2CH2PPh2, by reversible addition of thallium() β-diketonates to the complex cation [Pt3(µ3-CO)(µ-dppm)3]2ϩ,
is reported. The thallium() units are easily displaced from platinum by halide ions XϪ (X = Cl, Br, I) to give
[Pt3(µ3-CO)(µ3-X)(µ-dppm)3]ϩ, or by SnCl3Ϫ to give [Pt3(µ3-CO)(µ3-SnCl3)(µ-dppm)3]ϩ. With trifluoroacetate there
was an equilibrium with [Pt3(µ3-CO)(µ3-O2CCF3)(µ-dppm)3]ϩ and [Pt3{µ3-Tl(diketonate)(O2CCF3)}(µ3-CO)-
(µ-dppm)3]ϩ. The structures of two Pt3Tl clusters are reported, and the Pt3Tl unit is shown to be tetrahedral.
Table 1 Selected 31P NMR data for the complexes
Introduction
1J(PtP)
2J(TlP)
3J(PP)
There has been much interest in the use of thallium() as a
ligand in late transition metal chemistry,1–17 and many of the
known examples involve PtTl bonding.1–13 Most Pt–Tl bonded
complexes contain simple Pt–Tl or Pt–Tl–Pt units4,6–9,11–13 but
Tl–Pt–Tl units are also known.5,10 Platinum–thallium bonds in
cluster complexes are known as depicted in Chart 1,1–3 but the
Complex
δ(P)
2a
2b
2c
2d
2e
2f
Ϫ1.97
Ϫ1.27
Ϫ2.44
Ϫ0.10
Ϫ1.41
Ϫ1.85
Ϫ0.28
Ϫ1.71
3745
3765
3783
3754
3752
3766
3774
3757
487
412
485
459
485
465
463
465
140
110
100
110
100
130
150
100
2g
2h
Chart 1 Some clusters having Pt3Tl units.
only structurally characterized Pt3Tl complex is [Pt3(µ3-Tl)-
(µ-CO)3(PCy3)3]ϩ, isolated as the [RhCl2(cod)]Ϫ salt, A in Chart
1.1 Complex A has d(PtPt) = 2.667(1)–2.668(1) and d(PtTl) =
3.034(1)–3.047(1) Å so is regarded as having a distorted
tetrahedral core.1 Complex C (Chart 1) has an encapsulated
thallium() ion bridging two Pt3 triangles, with d(PtPt) =
2.658(3)–2.682(3) and d(PtTl) = 2.860(3)–2.992(3) Å.3 The
complex [Pt3(µ3-CO)(µ-dppm)3]2ϩ, 1,18 forms bimetallic cluster
complexes with many other main group and transition elem-
ents, including the Pt3ReTl complex B (Chart 1), which was
characterized by its spectroscopic properties.2 Thallium() may
act as a 2-electron donor using its 6s2 electrons, but it may also
act as an electrophilic group, accepting an electron pair from an
electron-rich metal into an empty 6p orbital.1–17 It is possible
that both of these forms of bonding may contribute to the
metal–thallium bond, resulting in little net electron transfer.
Since there are few Pt3Tl cluster complexes, it was of interest to
extend the series of known complexes by studying the binding
of thallium() directly to complex 1,18 and this article reports
that thallium() can bind easily and reversibly to give a series of
cluster complexes containing tetrahedral Pt3Tl units.
Scheme 1 Synthesis of the Pt3Tl clusters.
1, is shown in Scheme 1. The reactions to give complexes
[Pt3{µ3-Tl(diketonate)(OH2)}(µ3-CO)(µ-dppm)3][PF6]2, 2,
appeared to be quantitative when monitored by H and 31P
NMR spectroscopy, and the products could be isolated as
air-stable orange solids by precipitation from acetone solution.
However, the reactions are clearly equilibria and slow crystal-
lization from acetone–ether or acetone–pentane solutions
often gave single crystals of the precursor cluster complex 1.
Cyclopentadienylthallium() failed to form a complex with 1,
perhaps due to steric effects with the cyclopentadienyl group.
The presence of the Pt3Tl core in clusters 2 was clearly
demonstrated by the 31P NMR spectra, which showed the
presence of a coupling 2J(TlP) = 412–487 Hz (Table 1). A
typical 31P NMR spectrum is shown in Fig. 1. The spectra,
especially in the 195Pt satellite regions, were broad. The spectra
were essentially unchanged at low temperature, suggesting that
1
Results
1
The synthesis of new Pt3Tl complexes by addition of thallium()
β-diketonates19 to the complex cation [Pt3(µ3-CO)(µ-dppm)3]2ϩ,
the broadening is not a result of fluxionality. The H NMR
spectra were also broad, but showed the expected resonances
1212
J. Chem. Soc., Dalton Trans., 2002, 1212–1216
DOI: 10.1039/b107579a
This journal is © The Royal Society of Chemistry 2002

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Fig. 1 The 31P NMR spectrum of complex 2a. The central doublet
arises from 2J(TlP) and satellite spectra from 1J(PtP).
for the dppm and the β-diketonate ligands. In addition, a broad
singlet resonance at δ = 2.3–2.4 ppm was assigned to a water
ligand. None of the resonances showed coupling to thallium,
and it is possible that there is easy intermolecular exchange of
the diketonate and aqua ligands between thallium centres.
When the reactions of 1 with thallium diketonates are carried
out in dry acetone, it is likely that the acetone solvates are
formed but it has not been possible to isolate such complexes in
pure form or to grow crystals for structure determination. On
workup, the aqua complexes are isolated.
The binding of thallium() to platinum is evidently not
strong and attempted ligand substitution reactions at
thallium() tended to cause displacement from platinum. For
example, reactions with halide ions XϪ gave precipitation of
TlX and formation of [Pt3(µ3-CO)(µ3-X)(µ-dppm)3]ϩ, as
shown in Scheme 2. The thallium() centre in 2a was not
Fig. 2 A view of the structure of the dicationic cluster complex 2a,
with 30% probability ellipsoids. For clarity, thermal ellipsoids are not
shown for carbon atoms of the dppm ligands.
Fig. 3 A view of the structure of the cationic cluster complex 3, with
30% probability ellipsoids.
(µ3-CO)(µ-dppm)3]ϩ, each of which has a roughly tetrahedral
core.20
In terms of bonding, the units Tl(OH2)(diketonate) and
[Tl(O2CCF3)(diketonate)]Ϫ can be thought of as having
thallium() with sp3 hybridization and a stereochemically active
lone pair of electrons, that is then donated to the a1 acceptor
orbital of the Pt3 triangle of complex 1 to form the tetrahedral
cluster. The donor group can be thought of as isoelectronic
with [SnX3]Ϫ or with PX3. The donor [SnX3]Ϫ forms a similar
cluster as shown in Scheme 2, and is evidently a better donor
than thallium(). We have attempted to prepare the analogous
lead() derivatives since these would be strictly isoelectronic
with thallium() but without success. It should also be noted
that the isoelectronic donors Hg() and Tl() behave somewhat
differently, as seen in Scheme 2. The neutral Hg() does not
take on extra ligands, whereas thallium() does. Thus, if the
clusters are considered as having the main group metal acting
as a 2-electron-donor to a Pt3 cluster, the Tl() and Hg() deriv-
atives are similar. However, considering them as tetranuclear
clusters, the mercury() and thallium() derivatives are 54- and
60-electron clusters respectively. In these complexes, it is
probably best to consider the main group metal as a 2-electron
donor.
Scheme 2 Reactions of the Pt3Tl clusters.
displaced by mercury() but it was displaced by SnCl3Ϫ. With
trifluoroacetate there was an equilibrium with [Pt3(µ3-CO)-
(µ3-O2CCF3)(µ-dppm)3]ϩ and [Pt3{µ3-Tl(diketonate)(O2CCF3)}-
(µ3-CO)(µ-dppm)3]ϩ, and crystals of complex 3 (Scheme 1) were
isolated from one such reaction.
The structures of complexes 2a and 3 were determined
crystallographically, and are shown in Fig. 2 and 3. Selected
bond parameters are given in Table 2. For both complexes, the
[Pt3{µ3-Tl}(µ3-CO)(µ-dppm)3] core of the cluster was clearly
defined but the ligands on thallium exhibited disorder and
the bond parameters for them are less precise. Both 2a and 3
contain a roughly tetrahedral Pt3Tl core with similar mean
distances d(PtPt) = 2.645 and 2.638 Å and d(PtTl) = 2.911 and
2.903 Å in 2a and 3 respectively. The mean distance d(PtTl) is
shorter than in complex A, Chart 1, of 3.038 Å but similar to
that in complex C of 2.932 Å.1,2 The cluster structure is similar
to those in [Pt3(µ3-Hg)(µ3-CO)(µ-dppm)3]2ϩ and in [Pt3(µ3-SnF3)-
J. Chem. Soc., Dalton Trans., 2002, 1212–1216
1213

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1
acac]; 2.18 [s, 6H, CH3, acac]; δ(31P) = Ϫ1.97 [d, 6P, J(PtP) =
Table 2 Selected bond lengths [Å] and angles [Њ] for [Pt3(µ3-CO)-
{µ3-Tl(acac)(OH2)}(µ-dppm)3][PF6]2ؒCH2Cl2, 2a, and [Pt3(µ3-CO){µ3-
Tl(MeCOCHCOBu)(OCOCF3)}(µ-dppm)3][PF6]ؒ0.75Me2CO, 3
3745 Hz, 2J(TlP) = 487 Hz, 3J(PP) = 145 Hz, dppm]. Anal. Calc.
for: C81H75F12O4P8Pt3 Tl: C, 40.9; H, 3.2. Found: C, 41.2; H,
3.1%.
2a
3
[Pt3{ꢀ3-Tl(hfac)(OH2)}(ꢀ3-CO)(ꢀ-dppm)3][PF6]2 (2b). This
was prepared similarly but using Tl(hfac). The complex was
isolated as an orange solid in 62% yield. IR: ν(CO) 1790 (m)
cmϪ1. NMR: δ(1H) = 6.2 [m, 3H, HaCP2, dppm]; 5.9 [s, 1H, CH,
hfac]; 5.8 [m, 3H, HbCP2, dppm]; δ(19F) = Ϫ2.75 [d, 12F, 1J(PF)
= 175 Hz, PF6]; Ϫ77.7 [s, 6F, CF3, hfac]; δ(31P) = Ϫ1.27 [d,
Pt(1)–Pt(2)
Pt(1)–Pt(3)
Pt(2)–Pt(3)
Pt(1)–Tl
Pt(2)–Tl
Pt(3)–Tl
Pt(1)–C(1)
Pt(2)–C(1)
Pt(3)–C(1)
Tl–O(a)
Tl–O(b)
Tl–O(c)
2.642(1)
2.655(2)
2.639(2)
2.894(3)
2.891(3)
2.947(1)
2.17(4)
2.17(4)
2.26(2)
2.58(3)
2.26(3)
2.51(2)
2.640(1)
2.632(1)
2.642(1)
2.867(1)
2.906(1)
2.935(1)
2.18(2)
2.14(2)
2.21(2)
2.27(2)
2.30(2)
2.39(2)
2
3
1J(PtP) = 3765 Hz, J(TlP) = 412 Hz, J(PP) = 108 Hz, dppm].
Anal. Calc. for C81H69F18O4P8Pt3Tl: C, 39.2; H, 2.7. Found: C,
39.4; H, 2.5%.
[Pt3{ꢀ3-Tl(etac)(OH2)}(ꢀ3-CO)(ꢀ-dppm)3][PF6]2 (2c). This
was prepared similarly from Tl(etac). The orange product was
isolated in 58% yield. IR: ν(CO) 1790 (s) cmϪ1. NMR: δ(1H) =
6.35 [m, 3H, HaCP2, dppm]; 5.7 [m, 3H, HbCP2, dppm]; 5.5 [s,
1H, CH, etac]; 2.3 [br, 4H, CH2, etac]; 1.05 [t, 6H, J(HH) =
Pt(2)–Pt(1)–Pt(3)
Pt(3)–Pt(2)–Pt(1)
Pt(2)–Pt(3)–Pt(1)
Pt(2)–Pt(1)–Tl
Pt(3)–Pt(1)–Tl
Pt(3)–Pt(2)–Tl
Pt(1)–Pt(2)–Tl
Pt(2)–Pt(3)–Tl
Pt(1)–Pt(3)–Tl
Pt(2)–Tl–Pt(1)
Pt(2)–Tl–Pt(3)
Pt(1)–Tl–Pt(3)
59.76(8)
60.37(8)
59.87(3)
62.76(10)
63.99(6)
64.22(6)
62.89(10)
62.04(6)
61.95(7)
54.34(3)
53.73(5)
54.06(5)
60.14(3)
59.77(3)
60.09(3)
63.54(3)
64.34(3)
63.67(3)
62.03(3)
62.55(3)
61.71(3)
54.43(2)
53.78(2)
53.94(2)
1
7 Hz, CH3, etac]; δ(31P) = Ϫ2.44 [d, 6P, J(PtP) = 3783 Hz,
2J(TlP) = 485 Hz, 3J(PP) = 85 Hz, dppm]. Anal. Calc. for:
C83H79F12O4P8Pt3Tl: C, 41.4; H, 3.3. Found: C, 41.3; H, 3.0%.
[Pt3{ꢀ3-Tl(dpm)(OH2)}(ꢀ3-CO)(ꢀ-dppm)3][PF6]2 (2d). This
was prepared similarly from Tl(dpm) and isolated in 73% yield.
IR: ν(CO) 1780 (m) cmϪ1. NMR: δ(1H) = 5.8 [m, 3H, HaCP2,
dppm]; 5.2 [m, 3H, HbCP2, dppm]; 5.0 [s, 1H, CH, dpm]; 1.9 [s,
O(a), O(b) are in diketonate ligands, O(c) is in the aqua or trifluoro-
acetate ligand.
t
1
2
18H, Bu, dpm]; δ(31P) = Ϫ0.1 [d, J(PtP) = 3754 Hz, J(TlP) =
459 Hz, 3J(PP) = 108 Hz, dppm]. Anal. Calc. for C87H87-
F12O4P8Pt3Tl: C, 42.4; H, 3.6. Found: C, 42.6; H, 3.5%.
Experimental
[Pt3{ꢀ3-Tl(dbm)(OH2)}(ꢀ3-CO)(ꢀ-dppm)3][PF6]2 (2e). This
was prepared similarly using Tl(dbm) and isolated in 75% yield.
IR: ν(CO) = 1792 (s) cmϪ1. NMR: δ(1H) = 6.8 [m 3H, HaCP2,
dppm]; 6.5 [m, 3H, HbCP2, dppm]; 5.7 [s, 1H, CH, dbm]; δ(31P)
= Ϫ1.4 [d, 1J(PtP) = 3752 Hz, 2J(TlP) = 485 Hz, 3J(PP) = 98 Hz,
dppm]. Anal. Calc. for: C91H79F12O4P8Pt3Tl: C, 43.7; H, 3.2.
Found: C, 43.4; H, 3.0%.
All reactions were carried out under a N2 atmosphere using
Schlenk techniques. IR spectra were recorded as Nujol mulls
by using a Perkin-Elmer 2000 spectrometer. The H, 19F and
1
31P NMR spectra were recorded using a Varian Mercury 400 or
an Inova 400 spectrometer; the Pt3Tl complexes did not give
satisfactory 13C or 195Pt NMR spectra. Chemical shifts are
referenced to Me4Si (1H), CFCl3 (19F) or 85% H3PO4 (31P). The
complex [Pt3(µ3-CO)(µ-dppm)3][PF6]2 was prepared according
to the reported method,18 and thallium() diketonates were
prepared and characterized by the literature methods.19 Char-
[Pt3{ꢀ3-Tl(tfac)(OH2)}(ꢀ3-CO)(ꢀ-dppm)3][PF6]2 (2f ). This
was prepared similarly but using Tl(tfac) and the yellow–orange
product was isolated in 62% yield. IR: ν(CO) = 1792 (s) cmϪ1
.
NMR: δ(1H) = 6.3 [m, 3H, HaCP2, dppm]; 5.75 [m, 3H, HbCP2,
acterization data: Tl(acac), IR: ν(CO) 1571 (s), 1514 (m) cmϪ1
.
dppm]; 5.45 [s, 1H, CH, tfac]; 2.05 [s, 3H, CH3, tfac]; δ(19F) =
1H NMR: δ = 5.22 [s, 1H, CH]; 1.89 [s, 6H, CH3]; Tl(hfac), IR:
1
ν(CO) 1665 (s), 1557 (w), 1530 (m) cmϪ1. H NMR: δ = 5.47
1
Ϫ73.5 [d, 12F, J(PF) = 708 Hz, PF6]; Ϫ75.0 [s, 3F, CF3, tfac];
1
2
3
δ(31P) Ϫ1.85[d, J(PtP) = 3766 Hz, J(TlP) = 465 Hz, J(PP) =
135 Hz, dppm]. Anal. Calc. for C81H72F15O4P8Pt3Tl: C, 40.0; H,
3.0. Found: C, 39.6; H, 2.7%.
[s,1H, CH]; 19F NMR: δ = Ϫ76.9 [s, 6F, CF3]; Tl(etac), IR:
ν(CO) 1590 (s), 1509 (m) cmϪ1. 1H NMR: δ = 5.05 [s, 1H, CH];
2.07 [q, 4H, CH2]; 0.98 [t, 6H, CH3]; Tl(dpm), IR: ν(CO) 1602
(s), 1507 (w), 1498 (m) cmϪ1. H NMR: δ = 5.31 [s, 1H, CH];
1
0.94 [s, 18H, tBu]; Tl(dbm), IR: ν(CO) 1593 (s), 1550 (m) cmϪ1
.
[Pt3{ꢀ3-Tl(tbac)(OH2)}(ꢀ3-CO)(ꢀ-dppm)3][PF6]2 (2g). This
was prepared in a similar way using Tl(tbac) and isolated in
64% yield. IR: ν(CO) = 1790 (m) cmϪ1. NMR: δ(1H) = 6.35 [m,
3H, HaCP2, dppm]; 5.9 [s, 1H, CH, tbac]; 5.7 [m, 3H, HbCP2,
1H NMR: δ = 7.4–7.95 [m, 10H, Ph]; 6.05 [s, 1H, CH]; Tl(tfac);
IR: ν(CO) 1617 (s), 1516 (m) cmϪ1. H NMR: δ = 5.38 [s, 1H,
1
CH]; 1.96 [s, 3H, CH3]; 19F NMR: δ = Ϫ76.20 [s, CF3]; Tl(tbac),
IR: ν(CO) 1585 (s), 1548 (w), 1507 (s) cmϪ1. 1H NMR (acetone):
δ 5.29 [s, 1H, CH]; 1.88 [s, 3H, CH3]; 1.05 [s, 9H, tBu]; Tl(bzac),
IR: ν(CO) 1588 (s), 1569 (s) cmϪ1. 1H NMR (acetone): δ = 7.35–
7.82 [m, 5H, Ph]; 5.78 [s, 1H, CH]; 1.94 [s, 3H, CH3].
t
dppm]; 2.35 [s, 3H, CH3, tbac]; 1.25 [s, 9H, Bu, tbac]; δ(31P) =
Ϫ0.28 [d, 1J(PtP) = 3774 Hz, 2J(TlP) = 463 Hz, 3J(PP) = 190 Hz,
dppm]. Anal. Calc. for C84H81F12O4P8Pt3Tl: C, 41.7; H, 3.4.
Found: C, 41.5; H, 3.1%.
[Pt3{ꢀ3-Tl(bzac)(OH2)}(ꢀ3-CO)(ꢀ-dppm)3][PF6]2 (2h). This
Syntheses
was prepared similarly using Tl(bzac) and isolated as an
[Pt3{ꢀ3-Tl(acac)(OH2)}(ꢀ3-CO)(ꢀ-dppm)3][PF6]2 (2a). To a
solution of [Pt3(µ3-CO)(µ-dppm)3] [PF6]2 (50 mg, 0.024 mmol)
in acetone (5 mL) was added a solution of Tl(acac) (7.5 mg,
0.024 mmol) in acetone (5 mL). The resulting mixture was
stirred at room temperature for 0.5 h, then filtered and the
solution was concentrated to 3 mL. Ether was added to precip-
itate the complex product as an orange solid in 60% yield. IR:
ν(CO) = 1792 (s) cmϪ1. NMR in acetone-d6: δ(1H) = 6.3 [m, 3H,
HaCP2, dppm]; 5.8 [m, 3H, HbCP2, dppm]; 5.6 [s, 1H, CH,
orange–yellow solid in 75% yield. IR: ν(CO) = 1824 (s) cmϪ1
.
NMR: δ(1H) = 6.7 [s, 1H, CH, bzac]; 6.4 [m, 3H, HaCP2, dppm];
5.8 [m, 3H, HbCP2, dppm]; 2.3 [s, 3H, CH3, bzac]; δ(31P) =
Ϫ1.71 [d, 1J(PtP) = 3757 Hz, 2J(TlP) = 465 Hz, 3J(PP) = 102 Hz,
dppm]. Anal. Calc. for C86H77F12O4P8Pt3Tl: C, 42.3; H, 3.2.
Found: C, 42.0; H, 2.9%.
[Pt3(ꢀ3-Cl)(ꢀ3-CO)(ꢀ-dppm)3][PF6]. To a solution of complex
1 (40 mg) in methanol (10 mL) was added KCl (2.9 mg), and the
1214
J. Chem. Soc., Dalton Trans., 2002, 1212–1216

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Table 3 Crystal data and structure refinement for [Pt3(µ3-CO){µ3-Tl(acac)(OH2)}(µ-dppm)3][PF6]2ؒCH2Cl2, 2a, and [Pt3(µ3-CO){µ3-Tl(Me-
COCHCOBu)(OCOCF3)}(µ-dppm)3][PF6]ؒ0.75Me2CO, 3
Complex
2a
3
Formula
M
C81H74Cl2F12O3P8Pt3Tl
2431.70
C86H79F9O5P7Pt3Tlؒ0.75C3H6O
2413.48
T /K
293(2)
0.71073
Monoclinic, P21
13.459(3)
150(2)
0.71073
Monoclinic, P21/n
14.692(2)
Wavelength/Å
Crystal system, space group
a/Å
b/Å
c/Å
23.090(5)
14.721(3)
29.713(3)
21.744(2)
β/Њ
103.99(3)
4439(1), 2
1.819
99.054(4)
9373.6(18), 4
1.710
Volume/Å3, Z
Density (calc.)/Mg mϪ3
µ/mmϪ1
6.795
6.362
Ind. refl.
Abs. corr.
Data/restr./param.
Goof on F 2
R indices [I > 2σ(I )]
13736
16840
Integration
13736/1/428
1.104
Integration
16840/0/486
1.096
R1 = 0.0795, wR2 = 0.1899
R1 = 0.0944, wR2 = 0.2625
mixture was stirred for 2 h. The solvent volume was reduced
and water (5 mL) was added to precipitate the product, which
was washed with water and dried under vacuum. Yield 98%.
Anal. Calc. for C76H66ClF6OP7Pt: C, 46.9; H, 3.4. Found: C,
47.3; H, 3.8%. IR (Nujol): ν(CO) = 1767 cmϪ1. NMR in
acetone-d6: δ(1H) = 5.72, 5.92 [m, J(HH) = 14 Hz, CH2]; δ(31P) =
as a 60/40 mixture with isotropic fluorine atoms. The remain-
ing atoms of the molecule were refined anisotropically. The
hydrogen atoms were calculated geometrically and were riding
on their respective carbon atom. The solvent molecule was
refined isotropically complete with hydrogen atoms in the
model and refined to 75% occupancy.
The crystals of [Pt3(µ3-CO){µ3-Tl(acac)(OH2)}(µ-dppm)3]-
[PF6]2ؒCH2Cl2 were obtained from dichloromethane. Data were
collected and treated similarly, except that room temperature
collection was used. There was unresolved disorder of the acac
and H2O ligands and these were treated isotropically. All other
heavy atoms were anisotropic, with disorder in the anions.
There was also a high thermal parameter for methylene carbon
atom C(3), probably a result of unresolved disorder.
1
3
Ϫ17.6 [s, J(PtP) = 3700, J(PP) = 165, dppm]; δ(13C) = 197.0
[sept, 1J(PtC) = 890 Hz, 2J(PC) = 17 Hz, CO]
Similarly were prepared: [Pt3(µ3-Br)(µ3-CO)(µ-dppm)3][PF6].
Yield 97%. Anal. Calc. for C76H66BrF6OP7Pt: C, 45.9; H, 3.3.
Found: C, 45.1; H, 3.5%. IR (Nujol): ν(CO) = 1753 cmϪ1. NMR
in acetone-d6: δ(1H) = 5.71, 5.84 [m, J(HH) = 14 Hz, CH2]; δ(31P)
= Ϫ17.1 [s, 1J(PtP) = 3800, 3J(PP) = 160, dppm]; δ(13C) = 195.8
[sept, 1J(PtC) = 896 Hz, 2J(PC) = 20 Hz, CO]. [Pt3(µ3-I)-
(µ3-CO)(µ-dppm)3][PF6]. Yield 97%. Anal. Calc. for C76H66-
BrF6OP7Pt: C, 44.8; H, 3.3. Found: C, 44.5; H, 3.5%. IR
(Nujol): ν(CO) = 1767 cmϪ1. NMR in acetone-d6: δ(1H) = 5.57,
6.08 [m, J(HH) = 14 Hz, CH2]; δ(31P) = Ϫ17.8 [s, 1J(PtP) = 3890,
3J(PP) = 165]; δ(13C) = 192.7 [sept, 1J(PtC) = 850 Hz, 2J(PC) = 18
Hz, CO].
CCDC reference numbers 169369 and 169370.
See http://www.rsc.org/suppdata/dt/b1/b107579a/ for crystal-
lographic data in CIF or other electronic format.
Acknowledgements
We thank the NSERC for financial support and R. J. P. thanks
the Government of Canada for a Canada Research Chair.
Cluster exchange reactions
These reactions were carried out in NMR tubes containing
solutions of complex 2, and products were identified by their
1H and 31P NMR spectra. For reactions with halide ions, the
solutions were filtered to remove insoluble TlX and the prod-
ucts [Pt3(µ3-X)(µ3-CO)(µ-dppm)3][PF6] were identified by the
characteristic NMR spectra reported above.
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