Stepwise sulfuration of the terminal phosphide complex trans- [PtCl(PHCy2)2(PCy2)]

Article abstract of DOI:10.1002/ejic.200600174

The terminal phosphido complex trans-[PtCl(PHCy₂) ₂(PCy₂)] (1) has been prepared, exploiting the reversibility of the reaction with HCl, by action of 1,8-diazabicyclo[5.4.0] undec-7-ene (DBU) on [PtCl(PHCy₂)₃]Cl, and its reactivity towards elemental sulfur studied. The first product obtained by reaction of 1 with 1 equiv. of sulfur is trans-[PtCl(PHCy₂)₂{κP- P(S)-Cy₂}] (2), which rapidly isomerises in halogenated solvents into cis-[PtCl(PHCy₂)₂{κP-P(S)Cy₂}] (3). Further addition of sulfur causes the formation of a mixture of [Pt(κ²S,S′-PS₂Cy₂)-(PHCy ₂)₂]Cl (4) and [Pt(κ²S,S′-PS ₂Cy₂){κP-P(S)Cy₂}(PHCy₂)] (5), which could be selectively synthesised; the first upon sulfuration of pure 3 and the second by reaction of 4 with 1 equiv. of sulfur in the presence of DBU. Complex 5 can be further sulfurated to [Pt(κ²S,S′- PCy₂S₂)(κS-PCy₂S₂)(PHCy ₂)] (6), which is fluxional in solution and was also characterised by single-crystal X-ray diffraction. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

Full text of DOI:10.1002/ejic.200600174

FULL PAPER
DOI: 10.1002/ejic.200600174
Stepwise Sulfuration of the Terminal Phosphido Complex
trans-[PtCl(PHCy2)2(PCy2)]: Synthesis of [Pt(κ2S,SЈ-PS2Cy2)(PHCy2)2]Cl and
[Pt(κ2S,SЈ-PS2Cy2){κP-P(S)Cy2}(PHCy2)] and Crystal Structure of
[Pt(κ2-S,S-PCy2S2)(κ-S-PCy2S2)(PHCy2)]
Vito Gallo,[a] Mario Latronico,[a,b] Piero Mastrorilli,*[a] Cosimo Francesco Nobile,[a]
Giuseppe Ciccarella,[c] and Ulli Englert[d]
Keywords: Platinum / Terminal phosphides / Phosphanyl sulfides / Phosphanyldithioates / Phosphorus
The terminal phosphido complex trans-[PtCl(PHCy2)2(PCy2)]
(1) has been prepared, exploiting the reversibility of the reac-
tion with HCl, by action of 1,8-diazabicyclo[5.4.0]undec-7-
ene (DBU) on [PtCl(PHCy2)3]Cl, and its reactivity towards el-
emental sulfur studied. The first product obtained by reaction
of 1 with 1 equiv. of sulfur is trans-[PtCl(PHCy2)2{κP-P(S)-
Cy2}] (2), which rapidly isomerises in halogenated solvents
into cis-[PtCl(PHCy2)2{κP-P(S)Cy2}] (3). Further addition of
sulfur causes the formation of a mixture of [Pt(κ2S,SЈ-PS2Cy2)-
(PHCy2)2]Cl (4) and [Pt(κ2S,SЈ-PS2Cy2){κP-P(S)Cy2}(PHCy2)]
(5), which could be selectively synthesised; the first upon sul-
furation of pure 3 and the second by reaction of 4 with
1 equiv. of sulfur in the presence of DBU. Complex 5 can be
further sulfurated to [Pt(κ2S,SЈ-PCy2S2)(κS-PCy2S2)(PHCy2)]
(6), which is fluxional in solution and was also characterised
by single-crystal X-ray diffraction.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
Such high nucleophilicity has been exploited for the synthe-
sis of phosphido-bridged heterodimetallic species,[40] and is
also responsible for the ease of protonation of the three-
coordinate phosphorus atom[13,20,41–43] as well as for its re-
activity with MeI.[41,43–47]
The typical reaction of coordinated terminal phosphides
with chalcogens transforms the trivalent into a pentavalent
phosphorus atom bound to the chalcogen as in Scheme 1.
Introduction
Terminal phosphides are interesting albeit rare ligands,
the reactivity of which depends mainly on the characteris-
tics of the lone pair on the phosphorus atom. The first ter-
minal phosphido complexes were prepared in 1968 by reac-
–
–
tion of CpFe(CO)2 or CpMo(CO)3 with P(C6F5)2Cl to
give Cp(CO)2Fe[P(C6F5)2] and Cp(CO)3Mo[P(C6F5)2],
respectively.[1] From then on, a number of terminal phos-
phido complexes have been prepared mainly by two routes:
(i) the reaction of diorganometal phosphides with a metal
species;[2–16] (ii) the deprotonation of a coordinated phos-
phane bearing at least a P–H bond by means of an appropri-
ate base {1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),[17–19]
methoxide, OH–,[20–24] tBuO–,[25–29] [N(SiMe3)2]–,[30–32]
NEt3,[33] BuLi[34]} that, in some instances, was previously
coordinated onto the metal atom.[35–39]
Scheme 1. Typical addition of chalcogens E to coordinated ter-
minal phosphides.
Such reactivity is shown by Ir(CO)(Cl)2(PEt3)2(PF2) (re-
action with O2, S8 or Se),[48] (η5-C5H5)Ru(PEt3)2(PPh2) (re-
action with O2),[25] (η5-C5H5)Re(NO)(PPh3)2(PR2) (R =
Ph, tBu, reaction with O2),[28] (η5-C5H5)Fe(CO)2[P(CF3)2]
(reaction with S8),[49] (η5-C5H5)M(CO)3(PCl2) (M = Cr, re-
action with S8; M = W, reaction with S8, Se)[50] and (η5-
The reactivity of terminal phosphido complexes is deter-
mined by the presence of the lone pair on the phosphorus
atom, which renders such molecules highly nucleophilic.
[a] Dipartimento di Ingegneria delle Acque e di Chimica, Polytech- C5H5)M(CO)2(L)(PPh2) (L = CO or PMe3, M = Mo, reac-
tion with S8; M = W, reaction with S8, Se).[41,51]
nic of Bari,
Via Orabona 4, 70125 Bari, Italy
We have recently described the synthesis and characteri-
sation of trans-[PtCl(PHCy2)2(PCy2)Cl] (1) obtained by re-
action of cis-PtCl2(PHCy2)2 with LiPCy2.[52] Complex 1 is
stable under inert gases but reacts promptly with dry di-
oxygen to give the hydrogen-bound bis(phosphinito) com-
plex [PtCl(PHCy2){P(O)Cy2}2H][53] and with hydrogen per-
oxide to give trans-[PtCl(PHCy2)2{κP-P(O)Cy2}Cl].[54]
[b] Dipartimento di Ingegneria e Fisica dell’Ambiente,
Viale dell’Ateneo Lucano 10, 85100 Potenza, Italy
[c] Dipartimento di Ingegneria dell’Innovazione, University of
Lecce,
Via Monteroni, 73100 Lecce, Italy
[d] Institut für Anorganische Chemie der RWTH,
Landoltweg. 1, 52074 Aachen, Germany
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
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Stepwise Sulfuration of the Terminal Phosphido Complex trans-[PtCl(PHCy2)2(PCy2)]
FULL PAPER
Herein we describe the stepwise sulfuration of 1 leading
to the compounds trans-[PtCl(PHCy2)2{κP-P(S)Cy2}] (2),
cis-[PtCl(PHCy2)2{κP-P(S)Cy2}Cl] (3), [Pt(κ2S,SЈ-PS2Cy2)-
(PHCy2)2]Cl (4), [Pt(κ2S,SЈ-PCy2S2)(PHCy2){κP-P(S)Cy2}]
(5) and [Pt(κ2S,SЈ-PCy2S2)(κS-PCy2S2)(PHCy2)] (6).
Results and Discussion
Scheme 3.
Reversible Protonation of 1
Reaction of trans-[PtCl(PHCy2)2(PCy2)] (1) with gaseous
HCl results in the fast and complete protonation of the co-
ordinated terminal phosphide with formation of the cat-
ionic PtII complex [PtCl(PHCy2)3]Cl (7). In order to test
the reversibility of the protonation reaction of 1, a toluene
suspension of 7 was treated with DBU, leading to the quan-
titative formation of 1 as the only soluble product, so that
the reaction sequence shown in Scheme 2 represents the
most convenient way for preparing 1.
Complex 4, which incorporates two S atoms, showed two
31P{1H} NMR signals in CDCl3 at δ = 136.6 (2JP,Pt
=
151 Hz) and δ = 2.0 (1JP,Pt = 3048 Hz), which support a
structure in which the sulfur atoms are bound to the phos-
phide P atom and chelate the platinum atom. The remain-
ing coordination sites are occupied by two PHCy2 ligands,
mutually cis. Accordingly, the 195Pt{1H} NMR spectrum in
CDCl3 consists of a triplet (1JPt,P = 3048 Hz) of doublets
(2JPt,P = 151 Hz) centred at δ = –4596 ppm. Compound 4
can be therefore formulated as [Pt(κ2S,SЈ-PS2Cy2)-
(PHCy2)2]Cl, a dithiophosphinato complex of PtII. ESI-MS
analysis confirmed this formulation by comparison of the
measured isotope pattern centred at 852.35 Da with that
calculated on the basis of the natural abundances.
Recording the 31P{1H} and 1H NMR spectra of 4 in dif-
ferent solvents, we noticed that the resonance of (PS2Cy2)
remained almost unchanged (δ = 134–138 ppm), whilst the
chemical shift of the coordinated PHCy2 ligand ranged
from δ = –5.9 to 10.0 ppm (31P) and from δ = 4.3 to 6.8 ppm
(1H) (Table 1).
Scheme 2.
1
Table 1. 31P{1H} and H NMR spectroscopic data of 4 in different
solvents.
Reaction with S8
PS2
PH
–5.9
2.0
9.3
PH
Reaction of 1 with sulfur carried out in toluene at room
temperature using an S/Pt molar ratio of 1.0 resulted in the
formation of the P-bound thiophosphinito complex trans-
[PtCl(PHCy2)2{κP-P(S)Cy2}] (2).[54] Dissolving 2 in haloge-
nated solvents, the irreversible isomerisation into the ther-
modynamically favoured cis complex 3 took place as indi-
C6D6
CDCl3
CD2Cl2
CD3CN
134
137
139
140
6.83
5.15
4.32
4.43
10.0
Such behaviour could be explained invoking a hydrogen
cated in Scheme 3. This isomerisation was completed in bond interaction between the P–H of the cationic complex
5 min by heating the reaction mixture at 40 °C.
and the chloride anion, an interaction already found for
When an excess of sulfur (S/Pt molar ratio of 8) was [PtCl(PCy2H)3]Cl.[54] In order to confirm such a hypothesis
treated with 1 in toluene, the reaction led, after 1 h, to a we have compared the 35Cl NMR spectra recorded in
mixture of two new sulfur-containing platinum complexes, CD2Cl2 before and after the addition of CD3OD as a hy-
4 and 5, along with cis-PtCl2(PHCy2)2 and dicyclohex- drogen bond breaker. No signal could be observed in the
ylphosphane sulfide P(S)HCy2 (Scheme 4).
35Cl NMR spectrum recorded in CD2Cl2, as expected for a
Scheme 4.
Eur. J. Inorg. Chem. 2006, 2634–2641
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V. Gallo, M. Latronico, P. Mastrorilli, C. F. Nobile, G. Ciccarella, U. Englert
FULL PAPER
quadrupolar nucleus surrounded by an asymmetric electron at δ = 127.2, 48.4 and 38.9 ppm. Of these, that at δ =
cloud. However, the addition of a few drops of CD3OD 38.9 ppm can be attributed to a coordinated PHCy2 ligand
1
caused the rupture of the ion pairs, leaving the chloride (proton-coupled spectrum gave JP,H = 424 Hz) and that at
anion in a nearly symmetric solvation sphere, and permitted δ = 48.4 ppm can be attributed, on the basis of its chemical
1
the observation of a broad 35Cl NMR signal centred at δ shift and JP,Pt value (2977 Hz), to a P-bound P(S)Cy2 li-
= –18 ppm after the same number of scans (Figure 1).
gand cis to PHCy2. The remaining signal at δ = 127.2 ppm
is flanked by satellites from which a JP,Pt value of 137 Hz
2
was extracted and can be attributed to a chelating dithio-
phosphinate ligand, PS2Cy2. The 195Pt{1H} NMR spectrum
consists of a doublet of doublets of doublets centred at δ
= –4522 ppm and the proposed structure for 5 is [Pt(κ2S,SЈ-
PS2Cy2){κP-P(S)Cy2}(PHCy2)].
Complex 5 could be obtained in high yield by treating 4
with S8 in the presence of DBU as proton scavenger, and
showed P=S (of the thiophosphinite ligand) and PH IR
stretchings at 597 and 2366 cm–1 respectively. Comparison
of the IR features of complexes 2, 4 and 5 allowed us to
assign the νPS2 bands of 5 at 556 (νsym.) and 597 (νasym.).
Such assignments are consistent with those reported for
R2PS2 complexes.[55–57]
Figure 1. 35Cl NMR spectrum of 4 (39 MHz, 295 K); a) in CD2Cl2;
b) after the addition of a few drops of CD3OD.
Pure 4 could be isolated from the reaction of 3 with
1 equiv. S8 in dichloromethane at room temperature and
showed IR bands ascribable to PH (2272 cm–1) and PS2
stretchings (591, 553 cm–1).
Complex 5 incorporates three atoms of S and gives in
A mechanism for the reaction of 1 with excess sulfur in
C6D6 three 31P{1H} NMR signals flanked by 195Pt satellites CH2Cl2 is depicted in Scheme 5. The initially formed 2 par-
Scheme 5. Stepwise sulfuration of 1.
Scheme 6.
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Stepwise Sulfuration of the Terminal Phosphido Complex trans-[PtCl(PHCy2)2(PCy2)]
FULL PAPER
tially isomerises into 3. Both 2 and 3 can incorporate one 3) demonstrated the existence, for compound 6, of a rapid
more S atom yielding 4. The subsequent sulfuration of 4 interchange of bidentate and unidentate dithiophosphinates
into 5 requires a proton scavenger, as confirmed by the lack (Scheme 7).
of reaction between 4 and S8 in the absence of DBU.
In the reaction medium, possible proton scavengers are
the thiophosphinite complexes 2 and 3, whose products of
HCl formal addition are P(S)HCy2 and Pt(PHCy2)2Cl2, ef-
fectively found as byproducts (Scheme 6).
Compound 5 reacted slowly (several weeks) with elemen-
tal sulfur in toluene solution to give the bis(dithiophosphin-
ato)phosphane product Pt(κ2S,S-PCy2S2)(κS-PCy2S2)-
(PHCy2) (6, Scheme 5), which precipitated from the reac-
tion medium.
Complex 6 showed IR bands in the PS region (650–
500 cm–1) attributable to bidentate (620 and 527 cm–1) and
unidentate (598 and 559 cm–1) PCy2S2 ligands
(Table 2).[55,58]
Table 2. Characteristic IR bands in the PS region.
Complex
P(S)Cy2
PS2Cy2
Bidentate
PS2Cy2
Monodentate
ν
νsym.
νasym.
νsym.
νasym.
2
3
4
5
6
8
579
577
553
556
559
561
591
597
598
595
597
527
620
The 31P{1H} NMR spectrum of 6 in C6D6 showed three
resonances at δ = 124.8, 81.8 and 2.5 ppm ascribable to bi-
dentate PCy2S2, unidentate PCy2S2 and PHCy2, respec-
tively. Complexes of the general formula M(PS2)2(P) (where
PS2 represents a dithiophosphinato and P a tertiary phos-
phane) have long been known as the reaction products be-
tween M(PS2)2 and P in polar solvents[55] and, in fact, we
could prepare 6 in high yield also starting from [Pt(κ2S,SЈ-
PCy2S2)2] (8) and 1 equiv. of PHCy2 in toluene.
Figure 2. Variable-temperature 31P{1H} NMR spectra of 6 in 1,2-
dichlorobenzene.
Accordingly, the 31P EXSY experiment showed an in-
As already noticed for related complexes,[59–61] dynamic tense exchange cross-peak between the signals at δ =
31P{1H} and 195Pt{1H} NMR experiments (Figures 2 and 124.8 ppm (bidentate PS2Cy2) and δ = 81.8 ppm (uniden-
Figure 3. Variable-temperature 195Pt{1H} NMR spectra of 6 in CDCl3.
Eur. J. Inorg. Chem. 2006, 2634–2641
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V. Gallo, M. Latronico, P. Mastrorilli, C. F. Nobile, G. Ciccarella, U. Englert
FULL PAPER
Scheme 7.
tate PS2Cy2) (Figure 4). Variable-temperature 31P{1H} intermolecular C–H···S contacts in the range between 2.8
NMR spectra allowed us to calculate an activation ∆G‡ and 3.0 Å. Selected bond lengths and angles are listed in
value of 59 1 kJ/mol. Such a value is fully consistent with Table 3.
those obtained in the related complexes Pt(Me2PS2)(PPh3)
(∆G‡ = 56 kJ/mol),[60,62] Pt(Me2PS2)(PPh2C6F5) (∆G‡
=
55 kJ/mol)[62] and Pt{(OEt)2PS2}(PPh3) (∆G‡ = 52 kJ/
mol).[60,61]
Figure 5. Displacement ellipsoid plot of 6.[63] Ellipsoids are scaled
to 50% probability. Only the phosphorus-bonded hydrogen atom
is shown with arbitrary radius; the other H atoms are omitted for
clarity.
Table 3. Selected bond lengths [Å] and angles [°] for 6.
Pt(1)–P(3)
Pt(1)–S(3)
Pt(1)–S(1)
Pt(1)–S(2)
S(1)–P(1)
S(2)–P(1)
S(3)–P(2)
S(4)–P(2)
P(3)–Pt(1)–S(3)
P(3)–Pt(1)–S(1)
S(3)–Pt(1)–S(1)
P(3)–Pt(1)–S(2)
S(3)–Pt(1)–S(2)
S(1)–Pt(1)–S(2)
P(1)–S(1)–Pt(1)
P(1)–S(2)–Pt(1)
P(2)–S(3)–Pt(1)
P(3)–H(3)–S(4)
2.2136(15)
2.3024(15)
2.3419(16)
2.4134(15)
2.024(2)
2.017(2)
2.062(2)
1.964(2)
91.20(5)
93.89(5)
173.92(5)
176.44(6)
90.58(5)
84.16(5)
86.17(7)
84.44(7)
108.61(8)
136
Figure 4. 31P EXSY spectrum of 6 in C6D6.
Yellow crystals of 6 suitable for single-crystal X-ray dif-
fraction were deposited upon slow concentration of a tolu-
ene solution. Complex 6 crystallises in the monoclinic space
group P21/c with one complex molecule in the asymmetric
unit. The molecular structure, depicted in Figure 5, is char-
acterised by a distorted square-planar geometry around the
Pt atom. The Pt atom is bound to two PCy2S2– ligands, one
of which is chelating whereas the other one is unidentate.
The Pt–S(1) [2.3419(16) Å] and Pt–S(3) [2.3024(15) Å] bond
lengths are shorter than Pt–S(2) [2.4134(15) Å], as expected
on the basis of the different trans influences of P and S. The
structure of 6 resembles that found for the related complex
Pt[(OEt)2PS2]2(PPh3).[61] Both complexes show one uncoor-
dinated sulfur atom at a Pt···S distance of more than 4 Å.
The interaction between H(3) and the sulfur atom S(4) not
Conclusion
We have demonstrated that the sulfuration of complex 1
coordinated to Pt is certainly weak: the interatomic distance occurs stepwise, and involves first the terminal phosphide
amounts to 2.91 Å, to be compared with several intra- and giving rise to the formation of complexes 2, 3 and 4 and
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Stepwise Sulfuration of the Terminal Phosphido Complex trans-[PtCl(PHCy2)2(PCy2)]
FULL PAPER
tion of 3 (0.230 g, 0.268 mmol in 5 mL) at room temperature. After
2 h, the solvent was removed under reduced pressure and the resi-
due was treated with toluene (5 mL). Addition of n-hexane caused
the precipitation of 4 as a yellow solid, which was isolated by fil-
tration, washed with n-hexane and dried under vacuum. Yield:
0.170 g (71%). The complex was very soluble in halogenated sol-
vents and toluene and scarcely soluble in n-hexane. C36H68ClP3PtS2
(888.51): calcd. C 48.66, H 7.71, Cl 3.99, S 7.22; found 48.45, H
7.83, Cl 4.05, S 6.95. LC-MS: exact mass calcd. for the cationic
C36H68P3PtS2: 852.36 amu; found 852. M.p. 214 °C (dec.). IR (Nu-
subsequently one of the coordinated PHCy2 ligands with
formation of products 5 and 6.
Experimental Section
General: All manipulations were carried out under pure argon,
using freshly distilled and oxygen-free solvents. Dicyclohexylphos-
phane (Strem) and PtCl2 (Acros) were used as received. Complexes
2 and 7 were prepared as described elsewhere.[54] Melting points
were determined with Gallenkamp equipment and are uncorrected.
C, H and S elemental analyses were carried out with a Eurovector
CHNS-O Elemental Analyser. Cl elemental analysis was performed
by potentiometric titration using a Metrohm DMS Titrino. Infra-
red spectra were recorded with a Bruker Vector 22 spectrometer.
All the ESI-MS spectra were recorded with an Agilent LC-MS SL
series instrument adopting the following general conditions: elec-
trospray, positive ions, flow rate 0.200 mL/min, drying gas flow
4.0 L/min, nebuliser pressure 25 psi, drying gas temperature 300 °C,
capillary voltage 4000 V, mass range m/z = 400–1400. CH2Cl2 solu-
tions of the complexes were infused with a Cole-Parmer syringe
pump. The isotopic pattern was calculated by the Isotope Pattern
Viewer software available free of charge from the www.surfacespec-
tra.com Web site. NMR spectra were recorded with a BRUKER
Avance DRX400 spectrometer; frequencies are referenced to Me4Si
(1H and 13C), 85% H3PO4 (31P), H2PtCl6 (195Pt) and aqueous 1 
NaCl (35Cl). The reported temperatures of variable-temperature
NMR experiments were calibrated from the chemical shift differ-
jol mull): νmax = 2274 (w, P–H), 1345 (w), 1296 (m), 1268 (m), 1201
˜
(w), 1172 (m), 1120 (m), 1074 (w), 1005 (s), 918 (s), 888 (m), 850
(m), 820 (m), 752 (w), 727 (m), 591 (m, νPS2), 553 (s, νPS2), 515
1
(m), 466 (s), 406 (m) cm–1. H NMR (400 MHz, CDCl3, 295 K): δ
1
2
= 4.19 (m, JP,H = 402, JPt,H = 88 Hz, PH) ppm. 31P{1H} NMR
2
(162 MHz, CDCl3, 295 K): δ = 136.6 (s, JP,Pt = 151 Hz, PS2Cy2),
2.0 (s, JP,Pt = 3048 Hz, PHCy2) ppm. 35Cl NMR (39 MHz,
1
CD2Cl2, 295 K): δ = –18 (br.) ppm. 195Pt{1H} NMR (86 MHz,
CDCl3, 295 K): δ = –4596 (td, 1JP–Pt = 3048, 2JP–Pt = 151 Hz) ppm.
[Pt(κ2S,SЈ-PS2Cy2){κP-P(S)Cy2}(PHCy2)] (5): DBU (30 µL,
0.202 mmol) was added to a stirred dichloromethane solution
(5 mL) containing 4 (0.180 g, 0.202 mmol) and sulfur (7.5 mg). Af-
ter 10 min, the solvent was removed under reduced pressure and
the residue was treated with toluene (5 mL). The resulting suspen-
sion was filtered and 5 was obtained as a white solid (0.16 g, 89%
yield) after evaporation of the filtrate under reduced pressure. The
complex is very soluble in toluene and halogenated solvents, and
scarcely soluble in hexane and methanol. C36H67P3PtS3 (884.11):
calcd. C 48.91, H 7.64, S 10.88; found C 48.67, H 7.54, S 11.08.
LC-MS: exact mass calcd. for C36H67P3PtS3: 883.33 amu; found
1
ence of the signals in the H NMR spectrum of a standard sample
of methanol. The uncertainty in the ∆G‡ value ( 1 kJ/mol) was
Tc
estimated on the basis of the assumption that there is an error of
5 °C in the determination of the coalescence temperature. 2D 31P
EXSY spectra were recorded with a gradient-selected NOESY
pulse program from Bruker (noesygpph) with a mixing time of 10
or 50 ms and a relaxation delay of 1.0 s. The spectra were phased
to give positive peaks along the diagonal.
trans-[Pt(PHCy2)2(PCy2)Cl] (1):[52] DBU (131 µL, 0.86 mmol) was
added to a suspension of 7 (0.74 g, 0.86 mmol in 15 mL of toluene)
and the mixture stirred at room temperature for 5 min. The re-
sulting yellow suspension was filtered and pure 1 was obtained as
a yellow solid after solvent evaporation (0.63 g, 0.77 mmol, 89%).
884 [M + H]+. M.p. 248–250°°C. IR (Nujol mull): ν
= 2366 (w,
˜
max
PH), 1342 (w), 1328 (w), 1296 (m), 1175 (m), 1111 (m), 1075 (m),
1025 (s), 1002 (s), 889 (m), 848 (s), 817 (m), 756 (m), 736 (s), 597
(s, νP=S and νPS2), 556 (s, νPS2), 510 (m), 467 (w), 403 (m), 400
1
(m), 352 (w), 316 (m) cm–1. H NMR (400 MHz, C6D6, 295 K): δ
1
2
= 5.24 (br. d, JP,H = 424, JPt,H = 72 Hz) ppm. 31P{1H} NMR
2
(162 MHz, C6D6, 295 K): δ = 127.2 (br., JP,Pt = 137 Hz, PS2Cy2),
1
1
48.4 [br., JP,Pt = 2977 Hz, P(S)Cy2], 38.9 (br., JP,Pt = 3977 Hz,
PHCy2) ppm. 195Pt{1H} NMR (86 MHz, C6D6, 295 K): δ = –4522
1
1
2
(ddd, JP,Pt = 3977, JP,Pt = 2977, JP,Pt = 137 Hz) ppm.
[Pt(κ2S,SЈ-PCy2S2)(κS-PCy2S2)(PHCy2)] (6): A toluene solution of
PHCy2 (0.180 mmol in 2 mL) was slowly added to an orange tolu-
ene suspension of 8 (0.133 g, 0.184 mmol in 5 mL). After 10 min,
the obtained yellow suspension was filtered, the filtrate was concen-
trated to dryness and the resulting yellow solid was washed with n-
hexane (3×2 mL). Yield: 0.128 g, 76%. Complex 6 is very soluble
in halogenated solvents, slightly soluble in toluene and scarcely sol-
uble in n-hexane. C36H67P3PtS4 (916.18): calcd. C 47.19, H 7.37, S
14.0; found C 47.25, H 7.45, S 14.4. LC-MS: exact mass calcd. for
C48H90OP4Pt2: 915.30 amu; found 916 [M + H]+, 718 [M – PHCy2
Isomerisation of trans-[Pt(PHCy2)2{P(S)Cy2}Cl] (2) into cis-
[Pt(PHCy2)2{P(S)Cy2}Cl] (3): A dichloromethane solution of 2 was
stirred at room temperature for 1 h. Pure 3 was obtained after evap-
oration of the solvent under reduced pressure. The complex is very
soluble in halogenated solvents, fairly soluble in toluene, and
scarcely soluble in hexane. C36H68ClP3PtS (856.44): calcd. C 50.49,
H 8.00, Cl 4.14, S 3.74; found C 50.92, H 7.85, Cl 4.35, S 3.72.
LC-MS: exact mass calcd. for C36H68ClP3PtS: 855.36 amu; found
856 [M + H]+. M.p. 186 °C (dec.). IR (Nujol mull): ν
= 2272
˜
max
+ H]+. M.p. 208–210 °C. IR (Nujol mull): ν
= 2367 (w, P–H),
(w, PH), 1344 (w), 1297 (m), 1268 (m), 1201 (m), 1176 (m), 1115
(m), 1074 (w), 1005 (s), 918 (m), 895 (m), 870 (m), 848 (m), 819
(w), 736 (s), 577 (s, P=S), 511 (m), 411 (w), 400 (w), 388 (w), 298
˜
max
1297 (w), 1267 (w), 1178 (m), 1113 (m), 1075 (w), 999 (m), 919 (w),
885 (m), 849 (m), 819 (m), 748 (m), 620 (s, ν of unidentate PS2),
598 (m, ν of bidentate PS2), 559 (s, ν of bidentate PS2), 527 (m, ν
of unidentate PS2), 473 (w), 356 (w), 310 (w) cm–1. 1H NMR
1
(m, Pt–Cl), 227 (m) cm–1. H NMR (400 MHz, CDCl3, 295 K): δ
= 5.39 (m, 1JP,H = 383 Hz, PH trans Cl), 5.22 [m, 1JP,H = 373, 2JH,Pt
= 67 Hz, PH trans P(S)] ppm. 31P{1H} NMR (162 MHz, CDCl3,
295 K): δ = 67.4 [dd, 1JP,Pt = 1733, 2JP,P = 252, 2JP,P = 16 Hz, P(S)],
1
(400 MHz, C6D6, 295 K): δ = 5.94 (br. m, JP,H = 417 Hz, PH)
ppm. 31P{1H} NMR (162 MHz, C6D6, 295 K): δ = 124.8 (br. s,
2JP,Pt = 195 Hz, κ2S,SЈ-PCy2S2), 81.8 (br. s, κS-PCy2S2), 2.5 (s,
1JP,Pt = 3551 Hz, PHCy2) ppm. 195Pt{1H} NMR (86 MHz, CDCl3,
1
1
2
11.6 (br. s, JP,Pt = 3540, P trans Cl), 10.9 [dd, JP,Pt = 2822, JP,P
= 252, 2JP,P = 14 Hz, P trans P(S)] ppm. 195Pt{1H} NMR (86 MHz,
CDCl3, 295 K): δ = –5329 (ddd, JP,Pt = 3540, JP,Pt = 2822, JP,Pt
1
1
1
2
265 K): δ = –4052 (ddd, 1JP,Pt = 3551, 2JP,Pt = 184, JP,Pt = 116 Hz)
= 1733 Hz) ppm.
ppm.
[Pt(κ2S,SЈ-PS2Cy2)(PHCy2)2]Cl (4): A dichloromethane solution of
Pt(κ2S,SЈ-PCy2S2)2 (8): Dicyclohexylphosphane sulfide,[64] pre-
sulfur (9.0 mg, in 2 mL) was slowly added to a stirred CH2Cl2 solu-
pared by addition of 1 equiv. of elemental sulfur to a toluene solu-
Eur. J. Inorg. Chem. 2006, 2634–2641
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
2639

V. Gallo, M. Latronico, P. Mastrorilli, C. F. Nobile, G. Ciccarella, U. Englert
FULL PAPER
tion of PHCy2 at room temperature, was converted into P(Cy)2-
S2Na by further reaction with 1 equiv. of sulfur and subsequent
deprotonation by NaH. NaP(Cy2S2) (0.193 g, 0.678 mmol)[65] was
then poured into an ethanol suspension of K2PtCl4 (0.141 g,
0,339 mmol in 5 mL) and the mixture was vigorously stirred at
room temperaturefor 24 h. Complex 8 was isolated by filtration as
a pale orange solid, washed with n-hexane (4×2 mL) and dried
under vacuum. Yield: 0.181 g, 74%. The complex is fairly soluble
in halogenated solvents and insoluble in hexane and ethanol.
C24H44P2PtS4 (717.90): calcd. C 40.15, H 6.18, S 17.87; found C
40.65, H 6.31, S 18.05. LC-MS: exact mass calcd. for C24H44P2PtS4:
717.14 amu; found 718 [M + H]+. M.p. 279 °C (dec.). IR (Nujol
Acknowledgments
The Italian M.I.U.R. (PRIN 2004, project 2004030719_005) is
gratefully acknowledged for financial support.
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Empirical formula
Formula mass
Temperature [K]
Wavelength [Å]
Crystal system
Space group
Unit cell dimensions:
a [Å]
b [Å]
C36H67P3PtS4
916.14
110(2)
0.71073
monoclinic
P21/c
15.731(2)
11.1000(16)
27.258(3)
121.060(5)
4077.2(9)
4
1.492
3.788
2.25–29.70
51300
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8705
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1.102
0.0581
0.1208
c [Å]
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2640
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 2634–2641

Stepwise Sulfuration of the Terminal Phosphido Complex trans-[PtCl(PHCy2)2(PCy2)]
FULL PAPER
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Eur. J. Inorg. Chem. 2006, 2634–2641
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
2641