On the reactivity of the platina-β-diketone [Pt2{(COMe) 2H}2(μ-Cl)2] towards Ph2PCH 2CH2CH2SOxPh (x = 0, 2)

Article abstract of DOI:10.1002/zaac.201000344

The reaction of the electronically unsaturated platina-β-diketone [Pt₂{(COMe)₂H}₂(μ-Cl)₂] (1) with Ph₂PCH₂CH₂CH₂SPh (2) leads selectively to the formation of the acetyl(chlorido) platinum(II) complex (SP-4-3)-[Pt(COMe)Cl(Ph₂PCH₂CH₂CH ₂SPh-κP,κS)] (4) having the γ- phosphinofunctionalized propyl phenyl sulfide coordinated in a bidentate fashion (κP,κS). In boiling benzene complex 4 undergoes decarbonylation yielding the methyl(chlorido) platinum(II) complex (SP-4-3)-[PtMeCl(Ph ₂PCH₂CH₂CH₂SPh-κP,κS)] (6). However, the reaction of 1 with the analogous γ- diphenylphosphinofunctionalized propyl phenyl sulfone Ph₂PCH ₂CH₂CH₂SO₂Ph (3) affords the acetyl(chlorido) platinum(II) complex (SP-4-4)-[Pt(COMe)Cl(Ph ₂PCH₂CH₂CH₂SO₂Ph- κP)₂] (5). In boiling benzene complex 5 undergoes a CO extrusion yielding (SP-4-4)-[PtMeCl(Ph₂PCH₂CH ₂CH₂SO₂Ph-κP)₂] (8) whereas in presence of 1 the formation of the carbonyl complex (SP-4-3)-[PtMeCl(CO) (Ph₂PCH₂CH₂CH₂SO₂Ph- κP)] (7) is observed. Addition of Ag[BF₄] to complex 5 leads to the formation of the cationic methyl(carbonyl) platinum(II) complex (SP-4-1)-[PtMe(CO)(Ph₂PCH₂CH₂CH ₂SO₂Ph-κP)₂][BF₄] (9). All complexes were characterized by microanalysis and NMR spectroscopy ( ¹H, ¹³C, ³¹P) and complexes 4 and 6 additionally by single-crystal X-ray diffraction analyses.

Full text of DOI:10.1002/zaac.201000344

ARTICLE
DOI: 10.1002/zaac.201000344
On the Reactivity of the Platina-β-diketone [Pt2{(COMe)2H}2(μ-Cl)2]
Towards Ph2PCH2CH2CH2SOxPh (x = 0, 2)
Michael Block,[a] Martin Bette,[a] Christoph Wagner,[a] and Dirk Steinborn*[a]
Keywords: Platinum; Platinum complexes; Functionalized phosphane ligands; Decarbonylation; NMR sprectroscopy
Abstract. The reaction of the electronically unsaturated platina-β-dike- Cl(Ph2PCH2CH2CH2SO2Ph-κP)2] (5). In boiling benzene complex 5
tone [Pt2{(COMe)2H}2(μ-Cl)2] (1) with Ph2PCH2CH2CH2SPh (2) undergoes
leads selectively to the formation of the acetyl(chlorido) platinum(II) CH2CH2SO2Ph-κP)2] (8) whereas in presence of 1 the formation of
complex (SP-4-3)-[Pt(COMe)Cl(Ph2PCH2CH2CH2SPh-κP,κS)] (4) the carbonyl complex (SP-4-3)-[PtMeCl(CO)(Ph2PCH2CH2-
a CO extrusion yielding (SP-4-4)-[PtMeCl(Ph2PCH2-
having the γ-phosphinofunctionalized propyl phenyl sulfide coordi- CH2SO2Ph-κP)] (7) is observed. Addition of Ag[BF4] to complex 5
nated in a bidentate fashion (κP,κS). In boiling benzene complex 4 leads to the formation of the cationic methyl(carbonyl) platinum(II)
undergoes decarbonylation yielding the methyl(chlorido) platinum(II) complex
(SP-4-1)-[PtMe(CO)(Ph2PCH2CH2CH2SO2Ph-κP)2][BF4]
complex (SP-4-3)-[PtMeCl(Ph2PCH2CH2CH2SPh-κP,κS)] (6). How-
(9). All complexes were characterized by microanalysis and NMR
ever, the reaction of 1 with the analogous γ-diphenylphosphinofunc- spectroscopy (1H, 13C, 31P) and complexes 4 and 6 additionally by
tionalized propyl phenyl sulfone Ph2PCH2CH2CH2SO2Ph (3) affords single-crystal X-ray diffraction analyses.
the acetyl(chlorido) platinum(II) complex (SP-4-4)-[Pt(COMe)-
Here we report on reactions of the dinuclear platina-β-dike-
1 Introduction
tone [Pt2{(COMe)2H}2(μ-Cl)2] (1) with P∧SOx (x = 0, 2) type
Reactions of hexachloridoplatinic acid with n-butyl alcohol
and trimethylsilyl-substituted alkynes lead to the formation of
platina-β-diketones [Pt2{(COR)2H}2(μ-Cl)2] (R = alkyl) which
may be described as hydroxycarbene complexes stabilized by
strong intramolecular hydrogen bonds to acyl ligands, as
shown in Scheme 1 for the formation of the parent complex
1 (R = Me).[1] In contrast to Lukehart’s metalla-β-diketones
[LxM{(COR)2H}] (L = CO, Cp; M = Mo, Re, Fe,..; R = alkyl,
aryl),[2] platina-β-diketones exhibit a unique reactivity due to
their electronic unsaturation (16 valence electron complexes)
and their kinetically labile ligand sphere.[3] Thus, the platina-
β-diketone [Pt2{(COMe)2H}2(μ-Cl)2] (1) is found to react with
numerous monodentate and chelating donors L and L∧L yield-
ing, respectively, diacetyl(hydrido) platinum(IV) complexes of
type A and acetyl platinum(II) complexes of type B
(Scheme 1). In the case of hard/hard N∧N donors, the plati-
num(IV) complexes of type A proved to be thermally extraor-
dinarily stable,[4, 5] whereas with soft donors (P, P∧P, S∧S) type
A complexes could be detected NMR spectroscopically only
or remained unseen at all, thus only type B complexes could
be isolated.[6–8] The formation of the diacetyl platinum(II)
complexes of type C can be induced by addition of bases to
complexes A.[9, 10]
ligands Ph2PCH2CH2CH2SPh (2) and Ph2PCH2CH2CH2SO2Ph
(3) yielding mononuclear acetyl(chlorido) platinum(II) com-
plexes of type B as well as on their decarbonylation.
2 Results and Discussion
2.1 Syntheses
The dinuclear platina-β-diketone [Pt2{(COMe)2H}2(μ-Cl)2]
(1) was found to react in dichloromethane with
Ph2PCH2CH2CH2SPh (2) and Ph2PCH2CH2CH2SO2Ph (3) to
yield mononuclear acetyl(chlorido) platinum(II) complexes (4,
5, routes a/c, Scheme 2). In these reactions as well as in the
reactions described in the following, as a side product traces
of a black solid, most likely platinum black, were formed.
Complexes 4 and 5 were isolated in yields of > 70 % as color-
less air-stable products, which were characterized by NMR
(1H, 13C, 31P) and IR spectroscopy as well as by microanalyses
and single-crystal X-ray diffraction analysis (4).
The platinum complexes 4 and 5 were found to undergo a
decarbonylation reaction in boiling benzene within 2 hours,
thus yielding the methyl(chlorido) platinum(II) complexes 6
and 8 (routes b/d). The addition of Ag[BF4] to complex 5
(route e) led with precipitation of AgCl to the formation of the
methyl(carbonyl)platinum(II) complex 9. Complexes 6, 8 and
9 were isolated as colorless air-stable solids in yields between
70 and 78 % and fully characterized by microanalysis, 1H, 13C,
and 31P NMR spectroscopy as well as by single-crystal X-ray
diffraction analysis (6).
* Prof. Dr. D. Steinborn
E-Mail: dirk.steinborn@chemie.uni-halle.de
[a] Institut für Chemie
Martin-Luther-Universität Halle-Wittenberg
Kurt-Mothes-Straße 2
06120 Halle, Germany
206
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Z. Anorg. Allg. Chem. 2011, 637, 206–210

Reactivity of [Pt2{(COMe)2H}2(μ-Cl)2] Towards Ph2PCH2CH2CH2S(O)xPh
Scheme 1. Synthesis of the platina-β-diketone 1 and its reactivity towards monodentate and chelating ligands L and L∧L, respectively.
Scheme 2. Reactions of the platina-β-diketone 1 with γ-phosphinofunctionalized propyl phenyl sulfides and sulfones.
The reaction of the platina-β-diketone 1 with a deficiency of 2.2 Spectroscopic Investigations
the phosphinofunctionalized sulfone 3 (molar ratio 1:2) led –
in a fast reaction – to the formation of 5, whereas the half of
Selected NMR spectroscopic parameters of complexes 4–9 are
complex 1 remained unreacted (route f). This obtained mixture given in Table 1. The magnitudes of the 1JPt,P couplings in com-
was found to undergo – in a slow reaction within two days – plexes 4–9 are fully consistent with the trans influence order Cl
a decarbonylation reaction yielding the methyl(chlorido)car- < PR3 < Me because they were found to decrease from about
bonyl platinum(II) complex 7 (route g). In boiling benzene this 4500 Hz (4, 6) over 2500–3400 Hz (5, 8, 9) to ca 1450 Hz
reaction proceeded within two hours. Complex 7 was isolated (7). In the two acetyl(chlorido) platinum(II) complexes the 13C
(yield 82 %) as colorless air-stable solid and fully character- resonances of the methyl groups exhibited d+dd (4) and t+dt (5)
3
2
ized analytically and spectroscopically. Noteworthy, the pure patterns showing JP,C and JPt,C couplings of about 5/6 Hz and
complex 5, prepared according to route c, proved to be stable 165/215 Hz, respectively. However, in the 1H NMR spectra the
in dichloromethane solution at room temperature and reacted protons of the methyl groups appeared as singlet signals (δH
=
only in boiling benzene according to route d. 1.84/1.16) only. The carbonyl carbon atoms showed shifts in the
Table 1. Selected NMR spectroscopic data (δ in ppm, J in Hz) of complexes 4–9 bearing the ligands L1 (Ph2PCH2CH2CH2SPh) and L2
(Ph2PCH2CH2CH2SO2Ph), respectively.
Complex
δC (COMe) (2JP,C
)
δC (COCH3) (2JPt,C/3JP,C
)
δC (CO) (2JP,C
)
δC (CH3) (1JPt,C/2JP,C
)
δP (1JPt,P
)
[Pt(COMe)Cl(L1-κP,κS)]
[Pt(COMe)Cl(L2-κP)2]
[PtMeCl(L1-κP,κS)]
(4)
(5)
(6)
(7)
(8)
(9)
213.5 (6.8)
40.7 (167.0/4.7)
–
–
–4.1 (4765)
15.7 (3366)
4.0 (4407)
22.1 (1442)
23.2 (3056)
17.3 (2538)
215.3 (5.6)
44.2 (216.1/6.2)
–
–
–
–
–
–
–
–
–
–
–
–1.7 (616.0/5.9)
2.4 (479.7/87.4)
–13.0 (661.8/5.6)
2.4 (a)/6.5)
[PtMeCl(CO)(L2-κP)]
[PtMeCl(L2-κP)2]
165.1 (7.4)
–
[PtMe(CO)(L2-κP)2][BF4]
178.3 (5.3)
a) Not detected.
Z. Anorg. Allg. Chem. 2011, 206–210
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www.zaac.wiley-vch.de
207

M. Block, M. Bette, C. Wagner, D. Steinborn
ARTICLE
expected range (213.5/215.3 ppm, 4/5), but only 2JP,C couplings ular structures are shown in Figure 1 and Figure 2. Selected
1
(ca 6 Hz) due to weak intensity. The H and 13C resonances of structural parameters are given in the Figure captions.
the methyl ligands in complexes 6 and 8 exhibited strong high-
field shifts by, respectively, 1.2 and more than 40 ppm com-
pared to the resonances of the methyl group of the acetyl ligand
in complexes 4 and 5. Besides the expected coupling patterns
2
in complexes 6 (d+dd) and 8 (t+dt) the magnitudes of the JPt,H
1
couplings in the region of 70–80 Hz and of the JPt,C coupling
constants (600–700 Hz) unambiguously prove that the methyl
groups are directly bound to the platinum atom.
As expected, the shifts of the methyl ligands (1H, 13C) in com-
plexes 7 and 9 were also found in the highfield region (δH
=
1.10/0.50; δC = 2.4/2.4). Whereas the 1JPt,C coupling constant of
7 (480 Hz) is decreased by, respectively, 136 and 182 Hz com-
pared to the couplings in 6 and 8, it could not be detected in 9
Figure 2. Molecular structure of (SP-4-3)-[PtMeCl(Ph2PCH2CH2-
CH2SPh-κP,κS)] (6). The ellipsoids are shown with a probability of
50 %. Hydrogen atoms were omitted for clarity. Selected structural
parameters (distances in Å, angles in °): Pt–Cl 2.379(2), Pt–S 2.377(2),
Pt–P 2.204(2), Pt–C1 2.056(9), Cl–Pt–S 84.36(8), S–Pt–P 97.50(7), P–
Pt–C1 90.4(3), C1–Pt–Cl 87.8(3), Cl–Pt–P 176.52(8), S–Pt–C1
171.9(3).
2
due to bad signal-to-noise ratio. Noteworthy, the JP,C coupling
in the methyl(chlorido) carbonyl platinum(II) complex 7 is with
87.4 Hz very large but in the same region as reported for other
platinum(II) complexes bearing a methyl and a phosphane li-
gand in mutual trans position.[11–13] The resonances of the
carbonyl carbon atoms in 7 and 9 are in the expected region (δC
ca. 170) showing 2JP,C couplings of 7.4 and 5.3 Hz, respectively.
In the two complexes the platinum atoms adopt an almost
ideal square-planar configuration; only the S–Pt–P angles are
somewhat enlarged (98.90(9)°/97.50(7)°) due to the bite of the
chelating P∧S ligand. As expected, the Pt–Cl bonds (2.378(3)/
2.379(2) Å) are of the same length. The trans influence order
COMe > Me is reflected in a markedly longer Pt–S bond in 4
(2.435(3) Å) compared to that in 6 (2.377(2) Å). The Pt–C
bond lengths in 4 (2.02(1) Å) and 6 (2.056(9) Å) are analo-
gous to those in other platinum(II) complexes bearing a thio-
ether ligand in trans position to an acyl ligand[7, 14, 15] and a
methyl ligand,[16–18] respectively.
2.3 Structures
Crystals of 4 and 6 suitable for X-ray diffraction analyses
were obtained from dichloromethane solutions with a layer of
n-pentane at room temperature. In crystals monomeric com-
plexes without unusual intermolecular contacts (shortest inter-
molecular distance between non-hydrogen atoms: 3.46(2) Å,
C4···C14', 4; 3.44(2) Å, C20···C20', 6) were found. The molec-
2.4 Conclusion
Reactions
of
the
dinuclear
platina-β-diketone
[Pt2{(COMe)2H}2(μ-Cl)2] (1) with the γ-phosphinofunctional-
ized propyl phenyl sulfide (Ph2PCH2CH2CH2SPh, 2) and sul-
fone (Ph2PCH2CH2CH2SO2Ph, 3) lead via an unseen plati-
num(IV) intermediate of type A with reductive elimination of
1
acetaldehyde[4, 19] (detected H NMR spectroscopically) to the
formation of type B acetyl(chlorido) platinum(II) complexes
(4, 5) (Scheme 1). In complex 4, ligand 2 acts as a chelating
P∧S donor; analogous reactions were found with other biden-
tate P∧P[4] or N∧S[7] donors. In contrast, in complex 5 the phos-
phinofunctionalized sulfone 3 acts only as monodentate ligand
(κP), obviously due to a too low donor capability of the sul-
fonyl group. Its reactivity against 1 is analogous to that of non-
functionalized phosphanes PR3.[10]
In boiling benzene complexes 4 and 5 underwent an extru-
sion of CO yielding the respective methyl(chlorido) plati-
num(II) complexes 6 and 8, respectively. This decarbonylation
proceeds already at room temperature, if a “vacant” coordina-
tion site is generated by reaction of 5 either with Ag[BF4] or
Figure 1. Molecular structure of (SP-4-3)-[Pt(COMe)Cl(Ph2PCH2-
CH2CH2SPh-κP,κS)] (4). The ellipsoids are shown with a probability
of 50 %. Hydrogen atoms were omitted for clarity. Selected structural
parameters (distances in Å, angles in °): Pt–Cl 2.378(3), Pt–S 2.435(3),
Pt–P 2.217(3), Pt–C1 2.02(1), C1–C2 1.50(2), C1–O 1.226(1), Cl–Pt–
S 84.58(9), Cl–Pt–C1 88.5(3), S–Pt–P 98.90(9), P–Pt–C1 88.1(3), Cl–
Pt–P 176.5 (1), S–Pt–C1 172.9(3).
with the (unreacted) platina-β-diketone
1 (routes e/g,
Scheme 2). Here, the latter reaction was found to be diastereo-
selective yielding the (SP-4-3) isomer whereas the analogous
208
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© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 206–210

Reactivity of [Pt2{(COMe)2H}2(μ-Cl)2] Towards Ph2PCH2CH2CH2S(O)xPh
reaction using PPh3 instead of 3 proceeded non-diastereose- 3.3 Synthesis of [PtMeCl(Ph2PCH2CH2CH2SPh-κP,κS)] (6),
lective since the (SP-4-3) and the (SP-4-2) isomers of complex [PtMeCl(CO)(Ph2PCH2CH2CH2SO2Ph-κP)] (7) and
[PtClMe(CO)(PPh3)] were isolated in a ratio of 7:3.[6] On the [PtMeCl(Ph2PCH2CH2CH2SO2Ph-κP)2] (8)
other hand, in an analogous reaction using a phosphane with a
To a stirred suspension of 1 (100 mg, 0.16 mmol) in CH2Cl2 (5 mL)
low donor capability (P(C6F5)3) only the decarbonylated prod-
a solution of, respectively, 2 (108 mg, 0.32 mmol) and 3 (0.32 mmol
uct was formed.[11] Analogous decarbonylation reactions have
for the preparation of 7; 0.64 mmol for the preparation of 8) in CH2Cl2
also been reported on α-ketoacyl[20] and formyl platinum(II)
(2 mL) was added at –78 °C, allowed to warm to room temperature
complexes.[21] The results presented here give further insight
and stirred for further 30 minutes. After the solvent was evaporated in
into the reactivity of platina-β-diketones towards mono- and
bidentate ligands and readily access to novel acetyl, methyl
and carbonyl platinum(II) complexes.
vacuo, the residue was dissolved in benzene (2 mL) and the reaction
mixture was heated under reflux for two hours. After cooling to room
temperature the reaction mixture was filtered, n-pentane (5 mL) was
added to the filtrate, the precipitated solid was filtered off and washed
with n-pentane (3 × 3 mL). The crude products were re-precipitated
from chloroform/n-pentane (1:2), filtered off and dried in vacuo.
3 Experimental Section
(6) Yield: 136 mg (73 %). Anal. C22H24ClPPtS (582.00 g·mol–1): C,
45.40; H, 4.16; Found: C, 45.29; H, 4.28. 1H NMR (400 MHz,
3.1 General Remarks
3
2
CD2Cl2): δ = 0.59 (d+dd, JP,H = 4.15, JPt,H = 71.81 Hz, 3 H, CH3),
1.95–2.04 (m, 2 H, CH2CH2SPh), 2.49 (m, 2 H, CH2PPh2), 3.19 (m,
2 H, CH2SPh), 7.06–7.88 (m, 15 H, HPh). 13C NMR (100 MHz,
All reactions were performed in an argon atmosphere using the stand-
ard Schlenk techniques. Solvents were dried (Et2O, benzene and n-
pentane over Na/benzophenone, CH2Cl2 over CaH2) and distilled prior
to use. NMR spectra were recorded at 27 °C with Varian Gemini 200,
VXR 400 and Unity 500 spectrometers. Solvent signals (1H, 13C) were
used as internal references; δ(31P) is relative to external H3PO4 (85 %).
Multiplet signals in NMR spectra of higher order resulting in pseudo
triplets are denoted by 't'. IR spectra were recorded with a Bruker
Tensor 28 spectrometer with a Platinum ATR unit. Microanalyses were
performed by the University of Halle microanalytical laboratory
using CHNS-932 (LECO) elemental analyzer. The complex
[Pt2{(COMe)2H}2(μ-Cl)2] (1) as well as the γ-phosphinofunctionalized
sulfide (2) and sulfone (3) were prepared according to literature
methods.[1, 22, 23]
2
1
CD2Cl2): δ = –1.7 (d+dd, JP,C = 5.9, JPt,C = 616.0 Hz, CH3), 22.0 (s,
1
3
CH2CH2SPh), 25.4 (d, JP,C = 39.5 Hz, CH2PPh2), 36.9 (d, JP,C
=
2.7 Hz, CH2SPh), 128.5–133.5 (CPh). 31P NMR (81 MHz, CD2Cl2):
1
δ = 4.0 (s+d, JPt,P = 4407 Hz, PPh2).
(7) Yield: 168 mg (82 %). Anal. C23H24ClO3PPtS (642.01 g·mol–1):
C, 43.03; H, 3.77; Found: C, 42.87; H, 3.71. IR: ν = 2075 (s, CO)
3
cm–1. 1H NMR (400 MHz, CD2Cl2): δ = 1.10 (d+dd, JP,H = 7.65,
2JPt,H = 56.88 Hz, 3 H, CH3), 1.91–2.02 (m, 2 H, CH2CH2SO2Ph),
2.76–2.82 (m, 2 H, CH2PPh2), 3.19 (m, 2 H, CH2SO2Ph), 7.42–7.84
2
(m, 15 H, HPh). 13C NMR (100 MHz, CD2Cl2): δ = 2.4 (d+dd, JP,C
=
87.4, 1JPt,C = 479.7 Hz, CH3), 18.5 (d, 2JP,C = 2.7 Hz, CH2CH2SO2Ph),
1
3
24.3 (d, JP,C = 29.0 Hz, CH2PPh2), 56.7 (d, JP,C = 14.8 Hz,
CH2SO2Ph), 128.3–139.3 (CPh), 165.1 (d, JP,C = 7.4 Hz, CO). 31P
2
3.2 Synthesis of [Pt(COMe)Cl(Ph2PCH2CH2CH2SPh-κP,κS)]
(4) and [Pt(COMe)Cl(Ph2PCH2CH2CH2SO2Ph-κP)2] (5)
1
NMR (81 MHz, CD2Cl2): δ = 22.1 (s+d, JPt,P = 1442 Hz, PPh2).
(8) Yield: 123 mg (78 %). Anal. C43H45ClO4P2PtS2 (982.43 g·mol–1):
C, 52.57; H, 4.62; Found: C, 52.42; H, 4.77. 1H NMR (400 MHz,
To a stirred suspension of 1 (100 mg, 0.16 mmol) in CH2Cl2 (5 mL)
a solution of, respectively, 2 (108 mg, 0.32 mmol) and 3 (236 mg,
0.64 mmol) in CH2Cl2 (3 mL) was added at –78 °C and allowed to
warm to room temperature. After the addition of n-pentane (5 mL),
the precipitated solid was filtered off, washed with n-pentane (3 ×
3 mL) and dried in vacuo.
3
2
CDCl3): δ = –0.08 (t+dt, JP,H = 6.45, JPt,H = 80.64 Hz, 3 H, CH3),
2.08 (m, 4 H, CH2CH2SO2Ph), 2.74 (m, 4 H, CH2PPh2), 3.27 (m, 4 H,
CH2SO2Ph), 7.36–7.77 (m, 30 H, HPh). 13C NMR (100 MHz, CDCl3):
2
1
δ = –13.0 (t+dt, JP,C = 5.6, JPt,C = 661.8 Hz, CH3), 18.4 (s,
CH2CH2SO2Ph), 24.7 ('t', N = 35.2 Hz, CH2PPh2), 56.5 ('t', N =
14.6 Hz, CH2SO2Ph), 127.9–139.2 (CPh). 31P NMR (81 MHz, CDCl3):
(4) Yield: 150 mg (77 %). Anal. C23H24ClOPPtS (610.01 g·mol–1): C,
45.29; H, 3.97; Found: C, 44.61; H, 4.01. IR: ν = 1648 (s, CO) cm–1.
1H NMR (400 MHz, CDCl3): δ = 1.84 (s, 3 H, CH3), 1.93–2.04 (m,
2 H, CH2CH2SPh), 2.55 (m, 2 H, CH2PPh2), 3.15 (m, 2 H, CH2SPh),
7.23–7.73 (m, 15 H, HPh). 13C NMR (100 MHz, CDCl3): δ = 21.8 (s,
1
δ = 23.2 (s+d, JPt,P = 3056 Hz, PPh2).
3.4 Synthesis of [PtMe(CO)(Ph2PCH2CH2CH2SO2Ph-κP)2][BF4]
(9)
1
3
CH2CH2SPh), 25.2 (d, JP,C = 32.7 Hz, CH2PPh2), 36.0 (d, JP,C
=
3
2
2.9 Hz, CH2SPh), 40.7 (d+dd, JP,C = 4.7, JPt,C = 167.0 Hz, CH3),
To a stirred suspension of 1 (100 mg, 0.16 mmol) in CH2Cl2 (5 mL)
a solution of 3 (236 mg, 0.64 mmol) in CH2Cl2 (3 mL) was added at
–78 °C and allowed to warm to room temperature. Afterwards, the
solution was cooled to –78 °C again before a suspension of Ag[BF4]
(31 mg, 0.16 mmol) in CH2Cl2 (1 mL) was added. After warming to
room temperature and stirring for 30 minutes, the precipitated AgCl
was filtered off and the filtrate was stirred for 12 hours. The volume
was reduced to its half under reduced pressure, diethyl ether (5 mL)
was added, the precipitated solid was filtered off, washed with diethyl
ether (3 × 3 mL) and dried in vacuo.
128.5–133.2 (CPh), 213.5 (d, JP,C = 6.8 Hz, Pt–C). 31P NMR
2
1
(81 MHz, CDCl3): δ = –4.1 (s+d, JPt,P = 4765 Hz, PPh2).
(5) Yield: 232 mg (72 %). Anal. C44H45ClO5P2PtS2 (1010.44 g·mol–1):
C, 52.30; H, 4.49; Found: C, 52.01; H, 4.65. IR: ν = 1625 (s, CO)
1
cm–1. H NMR (400 MHz, CDCl3): δ = 1.16 (s, 3 H, CH3), 2.22 (m,
4 H, CH2CH2SO2Ph), 2.73 (m, 4 H, CH2PPh2), 3.28 (m, 4 H,
CH2SO2Ph), 7.36–7.82 (m, 30 H, HPh). 13C NMR (100 MHz, CDCl3):
δ = 18.7 (s, CH2CH2SO2Ph), 25.1 ('t', N = 35.0 Hz, CH2PPh2), 44.2
3
2
(t+dt, JP,C = 6.2, JPt,C = 216.1 Hz CH32), 56.5 ('t', N = 14.8 Hz,
CH2SO2Ph), 128.0–139.1 (CPh), 215.3 (t, JP,C = 5.6 Hz, Pt–C). 31P Yield: 119 mg (70 %). Anal. C44H45O5P2PtS2BF4 (1061.79 g·mol–1):
NMR (81 MHz, CDCl3): δ = 15.7 (s+d, JPt,P = 3366 Hz, PPh2).
1
C, 49.77; H, 4.27; Found: C, 49.66; H, 4.33. IR: ν = 2077 (s, CO)
Z. Anorg. Allg. Chem. 2011, 206–210
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de 209

M. Block, M. Bette, C. Wagner, D. Steinborn
ARTICLE
cm–1. 1H NMR (400 MHz, CD2Cl2): δ = 0.50 (t+dt, JP,H = 8.71, can be obtained free of charge on application to http://
2
1JPt,H = 61.97 Hz, 3 H, CH3), 2.06–2.15 (m, 4 H, CH2CH2SO2Ph), www.ccdc.cam.ac.uk/cgi-bin/catreq.cgi or from the Business & Ad-
2.98–3.04 (m, 4 H, CH2PPh2), 3.27 (m, 2 H, CH2SO2Ph), 7.52–7.83 ministration, Cambridge Crystallographic Data Centre, 12 Union Road,
(m, 30 H, HPh). 13C NMR (50 MHz, CD2Cl2): δ = 2.4 (t, JP,C
=
Cambridge, CB2 1EZ, UK; Fax: +44-1223-336033; or E-Mail:
2
6.5 Hz, CH3), 18.7 ('t', N = 25.7 Hz, CH2CH2SO2Ph), 25.5 ('t', N = admin@ccdc.cam.ac.uk.
35.7 Hz, CH2PPh2), 55.8 ('t', N = 15.9 Hz, CH2SO2Ph), 126.7–139.2
(CPh), 178.3 (t, 2JP,C = 5.3 Hz, CO). 31P NMR (81 MHz, CD2Cl2): δ =
1
References
17.3 (s+d, JPt,P = 2538 Hz, PPh2).
[1] D. Steinborn, M. Gerisch, K. Merzweiler, K. Schenzel, K. Pelz,
H. Bögel, J. Magull, Organometallics 1996, 15, 2454.
[2] C. M. Lukehart, J. V. Zeile, J. Am. Chem. Soc. 1976, 98, 2365.
[3] D. Steinborn, Dalton Trans. 2005, 2664.
[4] M. Gerisch, C. Bruhn, A. Vyater, J. A. Davies, D. Steinborn, Or-
ganometallics 1998, 17, 3101.
3.5 X-ray Crystallography
Single-crystals suitable for X-ray diffraction measurements of 4 and 6
were obtained from CH2Cl2 solutions with a layer of n-pentane. Inten-
sity data were collected with STOE diffractometers STADI-4 at 293(2)
K (4) and IPDS 2T at 200(2) K (6) using Mo-Kα radiation (λ =
0.7103 Å, graphite monochromator). A summary of the crystallo-
graphic data, the data collection parameters and the refinement parame-
ters is given in Table 2. Absorption corrections were applied numeri-
cally with X-RED32[24] (Tmin/Tmax 0.57/0.63, 4; 0.18/0.51, 6). The
structures were solved with direct methods using SHELXS-97[25] and
refined using full-matrix least-square routines against F2 with
SHELXL-97.[26] All non-hydrogen atoms were refined with anisotropic
displacement parameters and hydrogen atoms with isotropic ones.
Hydrogen atoms were placed in calculated positions according to the
riding model.
[5] A. Vyater, C. Wagner, K. Merzweiler, D. Steinborn, Organometal-
lics 2002, 21, 4369.
[6] M. Gerisch, F. W. Heinemann, C. Bruhn, J. Scholz, D. Steinborn,
Organometallics 1999, 18, 564.
[7] T. Gosavi, E. Rusanov, H. Schmidt, D. Steinborn, Inorg. Chim.
Acta 2004, 357, 1781.
[8] T. Gosavi, C. Wagner, H. Schmidt, D. Steinborn, J. Organomet.
Chem. 2005, 690, 3229.
[9] M. Werner, C. Bruhn, D. Steinborn, J. Organomet. Chem. 2008,
693, 2369.
[10] C. Albrecht, C. Wagner, D. Steinborn, Z. Anorg. Allg. Chem.
2008, 334, 2858.
[11] C. Albrecht, C. Wagner, K. Merzweiler, T. Lis, D. Steinborn,
Appl. Organomet. Chem. 2005, 19, 1155.
[12] S. Basu, N. Arulsamy, D. M. Roddick, Organometallics 2008, 27,
3659.
Crystallographic data (excluding structure factors) have been deposited
at the Cambridge Crystallographic Data Centre as supplementary pub-
lication nos. CCDC-793818 (4), CCDC-793819 (6). Copies of the data
[13] E. M. Pelczar, E. A. Nytko, M. A. Zhuravel, J. M. Smith, D. S.
Glueck, R. Sommer, C. D. Incarvito, A. L. Rheingold, Polyhe-
dron 2002, 21, 2409.
[14] Y. Minami, T. Kato, H. Kuniyasu, J. Terao, N. Kambe, Organome-
tallics 2006, 25, 2949.
Table 2. Crystallographic data, data collection parameters and refine-
ment parameters for 4 and 6.
[15] T. Kato, H. Kuniyasu, T. Kajiura, Y. Minami, A. Ohtaka, M. Kin-
omoto, J. Terao, H. Kurosawa, N. Kambe, Chem. Commun. 2006,
868.
4
6
[16] J. R. Dilworth, C. A. Maresca von Beckh W, S. I. Pascu, Dalton
Trans. 2005, 2151.
Empirical formula
C23H24ClOPPtS C22H24ClPPtS
Mr
609.99
581.98
[17] M. Rashidi, M. C. Jennings, R. J. Puddephatt, Organometallics
2003, 22, 2612.
Crystal system
monoclinic
C2/c
triclinic
¯
Space group
P1
[18] S. Ye, W. Kaim, M. Niemeyer, N. S. Hosmane, Organometallics
2005, 24, 794.
a /Å
24.687(3)
8.5402(8)
21.348(2)
9.2840(7)
9.7000(8)
12.844(1)
75.047(6)
86.022(6)
70.351(6)
1052.3(1)
2
b /Å
[19] D. Steinborn, T. Hoffmann, M. Gerisch, C. Bruhn, H. Schmidt,
K. Nordhoff, J. A. Davies, K. Kirschbaum, I. Jolk, Z. Anorg. Allg.
Chem. 2000, 626, 661.
c /Å
α /°
β /°
91.460(9)
[20] J.-T. Chen, Y.-S. Yeh, C.-S. Yang, F.-Y. Tsai, G.-L. Huang, B.-C.
Shu, T.-M. Huang, Y.-S. Chen, G.-H. Lee, M.-C. Cheng, C.-C.
Wang, Y. Wang, Organometallics 1994, 13, 4804.
[21] D. Vuzman, E. Poverenov, Y. Diskin-Posner, G. Leitus, L. J. W.
Shimon, D. Milstein, Dalton Trans. 2007, 5692.
[22] M. Block, C. Wagner, S. Gómez-Ruiz, D. Steinborn, Dalton
Trans. 2010, 39, 4636.
γ /°
V /Å3
4499.5(8)
8
Z
Dcalc /g·cm–3
μ(Mo-Kα) /mm–1
F(000)
1.801
1.837
6.531
6.973
2368
564
θ range /°
1.65–25.05
4648
2.82–29.22
18522
[23] M. Block, T. Kluge, M. Bette, J. Schmidt, D. Steinborn, Organo-
metallics in press.
[24] X-RED32 (version 1.07), Stoe Data Reduction Program, Stoe &
Cie GmbH, Darmstadt 2002.
[25] G. M. Sheldrick, SHELXS-97, Program for Crystal Structure So-
lution, University of Göttingen, Göttingen 1998.
[26] G. M. Sheldrick, SHELXL-97, Program for the Refinement of
Crystal Structures, University of Göttingen, Göttingen 1997.
Rfln. collected
Rfln. observed [I > 2σ(I)]
Rfln. independent
3006
3978
4625
5650
(Rint = 0.0373)
3978/0/253
1.099
(Rint = 0.0620)
5650/0/237
1.190
Data/restraints/parameters
Goodness-of-fit on F2
R1, wR2 [I > 2σ(I)]
R1, wR2 (all data)
0.0483, 0.1031
0.0762, 0.1220
0.0415, 0.0975
0.0546, 0.0994
Largest diff. peak and hole / 1.852 and –2.014 1.998 and –2.802
Received: September 16, 2010
Published Online: November 19, 2010
e·Å–3
210
www.zaac.wiley-vch.de
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 206–210