Reactions of triphenylbenzylphosphonium and tetraphenylstibonium chlorides with potassium tetrachloroplatinates in dimethylsulfoxide

Article abstract of DOI:10.1134/S1070363210090057

Platinum complexes [Ph₃PhCH₂P]⁺[(Me ₂S=O)PtCl₃]^- I and cis-Cl₂(Ph ₃Sb)(Me₂S=O)Pt II were synthesized by reaction of triphenylbenzylphosphonium and tetraphenylstibonium chlorides with potassium tetrachloroplatinate in DMSO. Crystal I is formed by triphenylbenzylphosphonium tetrahedral cations [P-C_Ph 1.791(4)-1.795(4) A, P-C _Alk 1.811(4) A; CPC 107.57(18)°-111.46(17)°] and by square anions [(Me₂S=O)PtCl₃]^- [Pt-Cl 2.3236(11), 2.2981(12), 2.2977(11) A; Pt-S 2.1950(10) A; trans-angles SPtCl 177.51(4)°, ClPtCl 178.74(4)°]. In a square-planar complex II [trans-angles SPtCl 178.01(6)°, ClPtSb 177.96(4)°] with central platinum atom the chlorine atoms [Pt-Cl 2.308(1), 2.350(1) A], triphenylstibine [Pt-Sb 2.5118(4) A] and dimethyl sulfoxide [Pt-S 2.195(1) A] molecules are coordinated. Compound II is a first example of mixed ligand complex of platinum(II), where in the coordination sphere of central atom the tertiary stibine is present along with DMSO ligand.

Full text of DOI:10.1134/S1070363210090057

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 9, pp. 1753–1757. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © V.V. Sharutin, V.S. Senchurin, A.P. Pakusina, O.K. Sharutina, B.B. Kunkurdonova, 2010, published in Zhurnal Obshchei Khimii,
2010, Vol. 80, No. 9, pp. 1434–1438.
Reactions of Triphenylbenzylphosphonium
and Tetraphenylstibonium Chlorides
with Potassium Tetrachloroplatinates in Dimethylsulfoxide
V. V. Sharutin, V. S. Senchurin, A. P. Pakusina, O. K. Sharutina, and B. B. Kunkurdonova
Blagoveshchensk State Pedagogical University, ul. Lenina 104, Blagoveshchensk, 675000 Russia
e-mail: vvsharutin@rambler.ru
Received November 10, 2009
Abstract—Platinum complexes [Ph3PhCH2P]+[(Me2S=O)PtCl3]– I and cis-Cl2(Ph3Sb)(Me2S=O)Pt II were
synthesized by reaction of triphenylbenzylphosphonium and tetraphenylstibonium chlorides with potassium tetrachloro-
platinate in DMSO. Crystal I is formed by triphenylbenzylphosphonium tetrahedral cations [P–CPh 1.791(4)–
1.795(4) Å, P–CAlk 1.811(4) Å; CPC 107.57(18)°–111.46(17)°] and by square anions [(Me2S=O)PtCl3]– [Pt–Cl
2.3236(11), 2.2981(12), 2.2977(11) Å; Pt–S 2.1950(10) Å; trans-angles SPtCl 177.51(4)°, ClPtCl 178.74(4)°].
In a square-planar complex II [trans-angles SPtCl 178.01(6)°, ClPtSb 177.96(4)°] with central platinum atom
the chlorine atoms [Pt–Cl 2.308(1), 2.350(1) Å], triphenylstibine [Pt–Sb 2.5118(4) Å] and dimethyl sulfoxide
[Pt–S 2.195(1) Å] molecules are coordinated. Compound II is a first example of mixed ligand complex of
platinum(II), where in the coordination sphere of central atom the tertiary stibine is present along with DMSO
ligand.
DOI: 10.1134/S1070363210090057
Numerous thermodynamically and kinetically
stable complexes of square symmetry are known, in
which platinum shows the most characteristic degree
of oxidation +2. The kinetic inertness of platinum
complexes makes their suitable to experimental study
of various types of isomerism and complex nature of
trans- and cis-effects. From this point of view, study of
reaction allowing the introduction of new ligands into
the platinum atom coordination sphere are of interest.
Platinum has a small affinity to oxygen ligands and it
predominantly binds with amines, sulfides, and
phosphines [1]. Platinum(II) complexes with tertiary
stibines were not studied earlier.
in DMSO gives rise to ionic complex [Ph3PhCH2P]+·
[(Me2S=O)PtCl3]– I. In this case the ligand exchange is
observed in the anion.
Ph3PhCH2PCl + K2[PtCl4]
Me2S=O
[Ph3PhCH2P]+[Pt(Me2S=O)Cl3]– + 2 KCl.
I
By X-ray analysis data, crystal I is formed by
tetrahedral triphenylbenzylphosphonium cations and
square anions of dimethylsulfoxidotrichloroplatinate
[(Me2S=O)PtCl3]–. Tetrahedral configuration of the
cation is not virtually distorted: lengths of bonds Р–С
differ a little from each other [P–CPh 1.791(4)–1.795(4) Å,
P–CAlk 1.811(4) Å], bond angles CPC [107.57(18)°–
111.46(17)°] almost not deviate from the theoretical
value. In the anion DMSO molecule is coordinated to
the central atom through sulfur (Fig. 1). Distances Pt–
Cl2 and Pt–Cl4 coincide practically for trans-arranged
chlorine atoms and are 2.2981(12) and 2.2977(11) Å.
The bond Pt–Cl1 [2.3236(11) Å] is labile, which is
explained by the presence of trans-effect of the
substituent Me2S=O. The bond length of Pt–S equals
Reaction of tetraphenylstibonium with potassium
hexachloroplatinate was established to proceed
through exchange mechanism to form ionic complex
with octahedral anion [Ph4Sb]2+[PtCl6]–2 [2]. In the
present work the reactions of triphenylbenzylphos-
phonium and tetraphenylstibonium chlorides with
potassium tetrachloroplatinates in DMSO have been
examined and results of the study of reaction products
structure are presented.
We found that reaction of tetraphenylbenzylphos-
phonium chloride with potassium tetrachloroplatinate
1753

1754
SHARUTIN et al.
C2P
C6B
C3P
C4P
C5B
C1P
C6P
C4B
C1B
C5P
P1
C2B
C3A
C3B
C2A
C1A
C6C
C1
C4A
C1C
C2C
C5C
C4C
C5A
O1
S1
C6A
C3C
C2S
C1S
Cl2
Cl4
Pt1
Cl1
Fig. 1. Structure of complex I.
C1
C134
O1
C133
C132
C131
C2
C135
C136
S1
Cl2
Sb1
Pt1
C121
C122
C123
C126
C125
Cl1
C111
C116
C113
C114
C115
Fig. 2. Structure of complex II.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 9 2010

REACTIONS OF TRIPHENYLBENZYLPHOSPHONIUM
1755
2.1950(10) Å. trans-Angles SPtCl1 [177.51(4)°] and
Cl2PtCl4 [178.74(4)°] are close to 180°. The planar
structure of anion is distorted: the sulfur atom is out-
of-plane of [PtCl3] by 0.13 Å. The oxygen atom of
DMSO molecule participates in the formation of a
hydrogen bond О···Н–С (О···Н 2.39 Å), where Н is the
para hydrogen atom of the phenyl ring of the benzyl
substituent.
Table 1. Crystallographic data, experimental parameters
and structure refinement for complexes I and II
Value
Parameter
I
II
М
732.96
100.0(2)
Rhombic
Pbca
697.17
120
Т, К
Crystal system
Space group
Triclinic
Р1¯
Reaction of tetraphenylstibonium chloride with
potassium tetrachloroplatinate in DMSO occurs
otherwise than the reaction of triphenylbenzylphos-
phonium chloride. On stirring the reaction mixture for
several minutes the reddish brown crystals of
potassium tetrachloroplatinate dissolved. The solution
becomes yellow, the neutral mixed ligand complex of
platinum(II) forms with triphenylstibine and DMSO
molecule in the coordination sphere of the central atom
of complex cis-Cl2(Ph3Sb)(Me2S=O)Pt II.
a, Å
15.0075(3)
18.3330(4)
19.6894(4)
10.4372(4)
10.7245(4)
12.7531(4)
65.1510(10)
88.4410(10)
61.9140(10)
1116.54(7)
2
b, Å
c, Å
a, deg
β, deg
g, deg
V, Å3
5417.19(19)
8
Z
ρcalc, g cm–3
μ, mm–1
1.797
2.074
5.632
7.807
Ph4SbCl + K2[PtCl4]
F(000)
2864
656
→ Cl2(Ph3Sb)(Me2S=O)Pt + PhCl + 2 KCl
Crystal form (size, mm)
Fragment
Plate
II
(0.26×0.13×0.08) (0.05×0.06×0.06)
Theta range for data
collection, deg
Index ranges
2.04–31.48
1.7–27.5
Solvent-free thermolysis of tetraphenylstibonium
halides at 250°С is known to proceed as reductive
elimination to give triphenylstibine and halobenzene
[3]. As we established, reduction Sb(V) → Sb(III) occurs
in the presence of platinum(II) salt at room temperature.
–21 ≤ h ≤ 13,
–21 ≤ k ≤ 26,
–21 ≤ l ≤ 26
7536
–13 ≤ h ≤ 13,
–13 ≤ k ≤ 13,
–16 ≤ l ≤ 10
8531
Reflections collected
Independent reflections
Variables refined
GOOF
As follows from X-ray analysis data, complex II
has a square-planar structure typical for Pt(II) [4].
Along with two chlorine ligands, coordination sphere
of the central atom contains DMSO molecule coor-
dinated through the sulfur atom, and triphenylstibine
molecule. Chlorine atoms are in the cis-position
relative to each other. trans-Angles Cl1PtS and Cl2PtSb
are 178.01(6) and 177.96(4) respectively. Angles
between cis-substituents SPtSb, SPtCl1, SbPtCl1,
Cl1PtCl2 equal 90.75(4), 90.24(6), 88.36(4), and 90.71(6)°
respectively.
5255
4968
309
237
1.014
0.992
R-indices on
F2 > 2σ(F2)
R1 0.0352,
wR2 0.0665
R1 0.0679,
wR2 0.0756
–2.158/2.776
R1 0.0328,
wR2 0.0543
R1 0.0583,
wR2 0.0607
–0.829/1.129
R-indices (all data)
Residual electron density
(min/max), e A–3
structure of complex II. The confirmation of trans-
effect rule is observed in complexes of Pt(II) of
general formula cis-Cl2L2Pt, in which bond length Pt–
Cl is somewhat smaller for DMSO platinum complex
(2.133, 2.251 Å, L = DMSO [5]) and longer for
similar platinum complexes with triarylstibine ligands
(2.292 Å, L = Ar3Sb [6]).
The bond length Pt–Sb is 2.5118(4) Å, the distance
Pt–S [2.1954(15) Å] coincides with similar distance in
complex I. Bond lengths Pt–Cl are unequal. The
shorter bond Pt–Cl1 [2.308(2) Å] corresponds to
chlorine ligand having DMSO molecule as trans-
molecule. Other distance Pt–Cl2 equals 2.350(2) Å,
that indicates stronger influence of triphenylstibine
ligand in comparison with dimethyl sulfoxide ligand.
A ligand with a strong trans-effect in the ligand
exchange orients into the trans-position to itself a
substituent with a weak effect as seen in the cis-
EXPERIMENTAL
Reaction of triphenylbenzylphosphonium chloride
with potassium tetrachloroplatinate. A mixture of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 9 2010

1756
SHARUTIN et al.
Table 2. Atomic coordinates (×104) and equivalent isotropic thermal parameters (×103) for structures I and II
Atom
x
y
z
Ueq, Å2
Atom
x
y
z
Ueq, Å2
I
II
Pt1
S1
5058.89(9)
6004.9(6)
509.9(6)
4572.76(9) 7309.35(8)
4451.5(6) 8152.1(5)
3186.4(6) 10191.1(5)
14.51(5)
15.8(2)
8.5(2)
Pt1
Sb1
S1
5482.9(3)
7076.5(4)
7467.8(16)
9312.4(3)
3133.8(2)
20.86(7)
20.14(10)
27.2(3)
10048.3(4) 1778.6(3)
P1
7279.6
(18)
4494.7(13)
Cl1
4080.5(7)
4653.8(8)
6397.8(6)
31.5(3)
Cl1
3419.4(16)
11507.9
(18)
1709.2(13)
31.3(4)
Cl2
Cl4
C1P
C4P
C6P
C3P
C5P
C2P
C4B
C2C
C1C
C6C
C4A
C2B
C3B
C6A
C5A
C4C
C3A
C3C
C5C
C6B
C2A
C1B
C1A
C1
5614.5(7)
4472.1(8)
1264(2)
2854(3)
1349(2)
2766(3)
2149(2)
1976(3)
–580(2)
348(2)
5703.3(7)
3452.3(6)
3289(2)
2628(2)
3004(2)
2915(2)
2674(2)
3242(2)
3224(2)
2592(2)
2461(2)
1743(2)
4177(2)
3770(2)
3764(2)
4225(3)
4133(2)
1296(2)
4340(2)
2004(2)
1167(2)
2705(2)
4427(2)
3244(2)
4359(2)
4074(2)
2694(2)
7035.6(6)
7580.1(6)
11468(2)
11066(2)
10815.7(19)
11716(2)
10615(2)
11916(2)
10564.9(19)
8895(2)
28.2(3)
28.4(3)
13.4(8)
17.9(9)
8.5(8)
Cl2
3957.4(18)
7571(7)
7297(7)
8903(4)
6063(7)
6472(7)
5861(7)
4848(7)
4419(7)
5009(7)
8200(6)
9129(7)
9836(7)
9594(7)
8665(7)
7975(6)
8698(6)
8212(7)
9250(8)
10703(8)
11164(7)
10168(7)
8611(2)
5471(7)
7247(8)
7163(5)
11861(7)
11549(7)
12748(8)
14272(7)
14607(7)
13406(7)
10887(6)
11366(7)
11928(8)
12049(8)
11616(7)
11016(7)
8116(6)
7254(7)
5974(7)
5612(7)
6486(7)
7743(7)
4351.3(14)
4758(6)
5887(5)
4286(4)
4(5)
34.3(4)
C1
41.0(17)
38.7(17)
33.3(10)
27.1(14)
29.5(14)
34.8(16)
36.0(16)
31.5(15)
29.2(14)
22.1(12)
29.9(15)
42.3(18)
43.3(18)
34.4(15)
26.6(14)
22.7(13)
28.4(14)
36.8(17)
37.9(18)
36.0(16)
31.1(15)
C2
O1
C111
C112
C113
C114
C115
C116
C121
C122
C123
C124
C125
C126
C131
C132
C133
C134
C135
C136
18.9(10)
14.7(9)
16.7(9)
9.4(8)
–944(5)
–2093(5)
–2310(5)
–1366(5)
–230(5)
2384(5)
1750(5)
2178(7)
3213(6)
3826(6)
3419(5)
1523(5)
1262(5)
1090(5)
1147(5)
1384(5)
1597(5)
12.6(8)
10.4(8)
15.1(9)
10.5(8)
16.5(9)
14.7(9)
20.9(10)
16.7(9)
18.6(9)
16.6(9)
17.0(9)
18.1(9)
16.0(9)
18.6(10)
17.4(9)
20.4(10)
11.2(8)
15.6(9)
26.2(8)
26.7(11)
28.9(11)
508(2)
9579(2)
557(2)
9821(2)
1704(2)
–2030(2)
–1179(2)
2820(3)
1936(3)
323(2)
9609(2)
10634(2)
10363(2)
8732(2)
8928(2)
8693(2)
2355(3)
261(2)
10084(2)
8452(2)
461(2)
9375(2)
–1700(2)
3237(3)
–2290(2)
3471(3)
744(2)
11289(2)
9885(2)
11097(2)
9212(2)
9829(2)
C5B
O1
C1S
C2S
–841(2)
5638.5(19)
6655(3)
6856(3)
11024(2)
4413.4(19) 8842.4(15)
3663(3)
5118(3)
8022(2)
8157(3)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 9 2010

REACTIONS OF TRIPHENYLBENZYLPHOSPHONIUM
1757
Table 3. Bond lengths and bond angles for structures I and
II
tetraphenylstibonium chloride, and 10 ml of DMSO.
Yield 0.22 g (79%), yellow crystals, mp 138°С. IR
spectrum, ν, cm–1: 3068, 3003, 2913, 1578, 1480,
1436, 1332, 1309, 1293, 1182, 1159, 1133, 1068,
1021, 996, 978, 937, 917, 850, 734, 693, 460, 441.
Found, %: С 41.49; Н 3.76. C20H21Cl2OPtS. Calcu-
lated, %: С 41.74; Н 3.65.
Bond d, Å
Angle ω, deg
I
Pt1–S1
2.1950(10)
2.3236(11)
2.2981(12)
2.2977(11)
1.468(3)
S1Pt1Cl1
S1Pt1Cl2
S1Pt1Cl4
Cl2Pt1Cl1
Cl4Pt1Cl1
Cl4Pt1Cl2
O1S1Pt1
O1S1C1S
O1S1C2S
C1SS1Pt1
C1SS1C2S
177.51(4)
Pt1–Cl(1)
Pt1–Cl2
Pt1–Cl4
S1–O1
91.95(4)
88.97(4)
89.45(5)
89.67(5)
178.74(4)
117.55(13)
107.6(2)
107.4(2)
109.33(17)
99.7(2)
IR spectra were recorded on an IR Fourier-spec-
trometer 1201 from KBr pellets. X-Ray diffraction
experiment was performed on an automatic four-circle
diffractometer Bruker–Nonius X8Apex (two-coordinate
CCD detector, МоKα irradiation, λ = 0.71073 Å,
graphite monochromator, φ-scanning). The extinction
was accounted for empirically (SADABS) [7]. Hyd-
rogen atoms positions were calculated geometrically
and involved into refinement in the rider model. The
structure was solved by the direct method and refined
by means of full-matrix least-squares in an anisotropic
approximation for non-hydrogen atoms (SHELX-97)
[8].
S1–C1S
S1–C2S
P1–C6P
P1–C4B
P1–C1C
P1–C1
1.762(4)
1.768(4)
1.791(4)
1.795(4)
1.794(4)
1.811(4)
II
Pt1–Sb1
Pt1–S1
2.5118(4)
2.195(1)
2.308(1)
2.350(1)
2.125(6)
2.099(6)
2.121(5)
1.773(6)
1.767(6)
1.469(4)
1.391(7)
1.389(8)
1.378(8)
1.369(8)
1.400(8)
1.368(8)
1.391(8)
1.387(7)
S1Pt1Sb1
90.75(4)
178.01(6)
90.24(6)
88.36(4)
90.71(6)
177.96(4)
119.2(2)
112.8(1)
102.0(2)
107.4(2)
112.6(1)
101.4(2)
110.0(2)
110.8(2)
101.8(3)
117.0(2)
109.0(3)
107.1(3)
S1Pt1Cl1
S1Pt1Cl2
Pt1–Cl1
Pt1–Cl2
Sb1–C111
Sb1–C121
Sb1–C131
S1–C1
S1–C2
S1–O1
C111–C112
Cl1Pt1Sb1
Cl1Pt1Cl2
Cl2Pt1Sb1
C111Sb1Pt1
C121Sb1Pt1
C121Sb1C111
C121Sb1C131
C131Sb1Pt1
C131Sb1C111
C1S1Pt1
The main crystallographic data are given in
Tables 1–3.
ACKNOWLEDGMENTS
Authors are grateful E.V. Peresypkina for X-ray
diffraction analysis of complexes I and II.
C
C
111–C116
112–C113
REFERNCES
C113–C114
C2S1Pt1
1. Cotton, F.A. and Wilkinson, G., Advanced Inorganic
Chemistry, New York: Wiley, 1988.
2. Sharutin, V.V., Senchurin, V.S., Fastovets, О.А.,
Pakusina, А.P, and Sharutina, О.K., Koord. Khim.,
2008, vol. 34, no. 5, p. 373.
C
C
C
C
114–C115
115–C116
121–C122
121–C126
C2S1C1
O1S1Pt1
O1S1C1
O1S1C2
3. Sharutin, V.V., Doctoral Sci. (Chem.) Dissert., Irkutsk,
1995, 40 p.
0.20 g of potassium tetrachloroplatinate, 0.19 g of
triphenylbenzylphosphonium chloride, and 10 ml of
DMSO was stirred at room temperature for 5 min. The
solvent was slowly evaporated. Yield 0.33 g (94%),
yellow crystals, mp 169оС. IR spectrum, ν, cm–1: 3052,
3022, 2927, 2883, 1583, 1484, 1436, 1316, 1126,
1109, 1024, 920, 838, 789, 745, 715, 696, 582, 514,
4. Poray-Koshits, М.А. and Kukina, G.A., Itogi nauki i
tekhniki. Kristallokhimiya. vol. 9, Moscow: VINITY,
1974, p. 7.
5. Shibayeva, R.I., Koord. Khim., 1985, vol. 11, no. 1,
p. 129.
6. Sharma, P., Perez, D., Rosas, N., et al., J. Organomet.
Chem., 2006, vol. 691, p. 579.
497, 445. Found, %:
С
43.76;
Н
3.69.
7. Sheldrick, G.M., SADABS, Program for Empirical X-
Ray Absorption Correction, Bruker–Nonius, 1990–
2004.
C27H28Cl3OPPtS. Calculated, %: С 44.23; Н 3.82.
Reaction of tetraphenylstibonium chloride with
potassium tetrachloroplatinate was performed similarly
with 0.20 g of potassium tetrachloroplatinate, 0.22 g of
8. Sheldrick, G.M., SHELX-97 Release 97-2, University of
Goettingen, Germany, 1998.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 9 2010