Pt(II) and Pd(II) complexes with (2-bromo-1-phenylvinyl)diphenylphosphine and tris(Z-styryl)phosphine

Article abstract of DOI:10.1007/s11176-005-0300-4

Methods were developed for selective synthesis of geometric isomers of Pt(II) and Pd(II) complexes with (2-bromo-1-phenylvinyl)diphenylphosphine and tris(Z-styryl)phosphine. 2005 Pleiades Publishing, Inc.

Full text of DOI:10.1007/s11176-005-0300-4

Russian Journal of General Chemistry, Vol. 75, No. 5, 2005, pp. 694 696. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 5, 2005,
pp. 734 737.
Original Russian Text Copyright
2005 by Reznikov, Savin, Krivchun, Skvortsov, Sukhov, Malysheva.
Pt(II) and Pd(II) Complexes
with (2-Bromo-1-phenylvinyl)diphenylphosphine
and Tris(Z-styryl)phosphine
A. I. Reznikov*, I. M. Savin*, M. N. Krivchun*,
N. K. Skvortsov*, B. G. Sukhov**, and S. F. Malysheva**
*St. Petersburg State Technological Institute (Technical University), St. Petersburg, Russia
**Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
Received July 6, 2004
Abstract Methods were developed for selective synthesis of geometric isomers of Pt(II) and Pd(II) com-
plexes with (2-bromo-1-phenylvinyl)diphenylphosphine and tris(Z-styryl)phosphine.
Transformations of unsaturated organophosphorus
compounds in the metal coordination sphere [1 3] and
catalytic processes involving transition metaphos-
methyl sulfoxide complex in excess, trans-dichloro-
bis[(2-bromo-1-phenylvinyl)diphenylphosphine]pla-
tinum(II) was formed exclusively. If the reaction was
phine complexes [4 6] are new fields of hetero- carried out with excess phosphine, the cis complex
organic chemistry. Therefore, synthesis of new com-
plexes containing unsaturated organophosphorus
ligands in the coordination sphere is of interest.
was obtained.
The reaction of potassium tetrachloroplatinate(II)
with tris(Z-styryl)phosphine taken in a small excess
yields exclusively trans-dichlorobis[tris(Z-styryl)-
phosphine]platinum(II).
We have previously reported on the synthesis of
complexes of Pt(II), Pd(II), and Ni(II) with diphenyl-
(1-cyclohexenyl)phosphine and diphenyl(1-phenyl-
vinyl)phosphine [7]. Proceeding with these studies,
we have prepared Pt(II) and Pd(II) complexes with
(2-bromo-1-phenylvinyl)diphenylphosphine and tris-
(Z-styryl)phosphine.
K2PtCl4 + 2(PhCH=CH)3P
trans-{PtCl2[(PhCH=CH)3P]2} + 2KCl.
At the same time, it is known [11, 12] that cis
complexes are usually formed under similar condi-
tions. Such an unusual reaction pathway may be due
to the steric hindrance to coordination of the bulky
phosphorus ligand.
The synthetic methods and X-ray data for non-
coordinated
(2-bromo-1-phenylvinyl)diphenylphos-
phine were published in [8]. Tris(Z-styryl)phosphine
can be readily prepared by direct phosphorylation of
phenylacetylene with elemental phosphorus in the
presence of strong bases [9, 10].
The structures of the isomeric products obtained
are confirmed by the (Pt Cl) stretching frequencies
and the JPtP coupling constants in the 31P NMR spec-
tra, characteristic of Pt(II) cis- and trans-bisphosphine
complexes [13].
The Pt(II) complexes with (2-bromo-1-phenylvinyl)-
diphenylphosphine were prepared from dichlorobis-
(dimethyl sulfoxide)platinum(II) by substitution of
sulfoxide in the coordination sphere with the cor-
responding phosphines.
An attempt to prepare Pt(II) bisphosphine com-
plexes by the substitution of the labile sulfoxide
ligands in the reaction of dichlorobis(dimethyl sulf-
oxide)platinum with tris(Z-styryl)phosphine leads,
according to the 31P NMR data, to a complex mixture
of products. In the spectrum of this mixture, we
tentatively assign a signal at 28.4 ppm with the
coupling constant JPtP 3507 Hz to the bisphosphine
complex of the cis structure.
[PtCl2(Me2SO)2] + 2Ph2PC(Ph)=CHBr
[PtCl2(Ph2PC(Ph)=CHBr)2] + 2Me2SO.
The geometry of the bisphosphine complex formed
depends on the ratio of the starting reactants. The
trends were similar to those in the reaction of dichlo-
robis(dimethyl sulfoxide)platinum(II) with diphenyl-
(1-cyclohexenyl)phosphine [7]. With the starting di-
The reaction of palladium(II) chloride with tris(Z-
styryl)phosphine in an acidic medium gives dichloro-
bis[tris(Z-styryl)phosphino]palladium(II).
1070-3632/05/7505-0694 2005 Pleiades Publishing, Inc.

Pt(II) AND Pd(II) COMPLEXES WITH (2-BROMO-1-PHENYLVINYL)DIPHENYLPHOSPHINE
695
PdCl24 + 2(PhCH=CH)3P
{PdCl2[(PhCH=CH)3P]2} + 2Cl .
Spectral characteristics of the transition metal complexes
with , -unsaturated phosphines and free ligands
1
In the H NMR spectra of trans-dichlorobis[tris-
(Z-styryl)phosphine]platinum(II) and trans-dichloro-
bis[tris(Z-styryl)phosphine]palladium(II), the effect of
the so-called virtual splitting of the vinyl proton
signals is observed. This effect is due to the additional
coupling with the trans-located phosphorus atom. A
similar effect was noted previously [13] for trans-di-
chlorobis(vinyldiphenylphosphine)palladium and was
,
JPtP
Hz
,
,
P
Compound
1
ppm
cm
Ph2PC(Ph)=CHBr
Z,Z,Z-(PhCH=CH)3P
5.29
59.0
trans-{PtCl2[Ph2PC(Ph)=CHBr]2} 29.0
cis-{PtCl2[Ph2PC(Ph)=CHBr]2} 21.1
2684 344
3708 305,
327
1
trans-{PdCl2[Ph2PC(Ph)=CHBr]2} 27.7
359
observed by us in the H NMR spectra of Pd(II) and
trans-{PtCl2[(PhCH=CH)3P]2}
trans-{PdCl2[(PhCH=CH)3P]2}
32.5
25.8
2401 344
358
Pt(II) trans complexes with diphenyl(1-cyclohexe-
nyl)phosphine and diphenyl(1-phenylvinyl)phosphine
[7].
1
Contrary to tris(Z-styryl)phosphine, the reaction
cm : 523 (0.358), 532 (0.360), 592 (0.877), 610
(0.577), 640 (0.640), 695 (0.222), 719 (0.337), 745
(0.275), 779 (0.213), 843 (0.438), 916 (0.511), 975
(0.619), 999 (0.750), 1028 (0.521), 1074 (0.550),
1159 (0.392), 1178 (0.393), 1225 (0.715), 1300
(0.819), 1319 (0.745), 1333 (0.759), 1358 (0.794),
1445 (0.295), 1492 (0.255), 1572 (0.368), 1594
(0.296), 2929 (0.915), 2986 (0.551), 3023 (0.446),
with
(2-bromo-1-phenylvinyl)diphenylphosphine
under the similar conditions is unselective, and the
product yield is low. Therefore, to prepare dichloro-
bis[(2-bromo-1-phenylvinyl)diphenylphosphine]pal-
ladium(II), we used the substitution of the nitrile by
phosphine in the coordination sphere of dichlorobis-
(benzonitrile)palladium(II).
1
3057 (0.429). H NMR spectrum, , ppm: 6.35 d (1H,
3
3
3
[PdCl2(PhCN)2] + 2Ph2PC(Ph)=CHBr
[PdCl2(Ph2PC(Ph)=CHBr)2] + 2PhCN.
CH=, JHH 13 Hz), 7.18 d.d (1H, CH=, JHH 13, JHP
24 Hz), 7.31 m, 7.59 m (5H, Ph). 59.0 ppm.
P
cis-Dichlorobis[(2-bromo-1-phenylvinyl)di-
phenylphosphine]platinum(II). (2-Bromo-1-phenyl-
vinyl)diphenylphosphine, 226 mg, was dissoved in
10 ml of chloroform, and 50.0 mg of dichlorobis(di-
methyl sulfoxide)platinum was added. The reaction
mixture was refluxed for 1 h. The starting complex
dissolved. After the reaction completion, the mixture
was filtered. The product was precipitated from the
filtrate with hexane. The precipitate was washed with
ethanol and diethyl ether and dried. Yield 41.7 mg
The phosphorus chemical shifts, coupling constants
JPtP, and (Pt Cl) and (Pd Cl) stretching frequencies
are listed in the table.
EXPERIMENTAL
The IR spectra were recorded on FSM-1201 (400
1
1
4000 cm ) and Hitachi FIS-3 (200 400 cm ) spec-
trometers. The 1H and 31P NMR spectra were
measured on a Bruker AC-200 spectrometer (working
frequences 200.132 and 81.026 MHz, respectively) in
CDCl3. The chemical shifts were measured against
TMS (1H) and 85% H3PO4 (31P).
1
(35%), mp 184 C. IR spectrum (KBr), , cm : 465
(0.794), 486 (0.829), 507 (0.728), 523 (0.803), 542
(0.716), 585 (0.731), 691 (0.585), 714 (0.651), 745
(0.734), 774 (0.804), 821 (0.922), 841 (0.943), 929
(0.910), 945 0.864), 1000 (0.877), 1028 (0.839), 1073
(0.865), 1096 (0.660), 1157 (0.898), 1188 (0.899),
1406 (0.895), 1435 (0.680), 1483 (0.833), 1572
(0.893), 1593 (0.897), 1648 (0.904), 1889 (0.941),
(2-Bromo-1-phenylvinyl)diphenylphosphine [8].
1
IR spectrum (KBr), , cm : 465 (0.315), 502 (0.125),
532 (0.377), 577 (0.301), 668 (0.314), 677 (0.288),
698 (0.035), 739 (0.077), 748 (0.158), 778 (0.148),
854 (0.552), 913 (0.100), 997 (0.407), 1028 (0.321),
1067 (0.279), 1094 (0.302), 1156 (0.390), 1304
(0.382), 1329 (0.393), 1404 (0.294), 1432 (0.091),
1445 (0.302), 1478 (0.194), 1489 (0.211), 1568
1
2853 (0.869), 2924 (0.869), 3053 (0.822). H NMR
spectrum, , ppm: 6.75 7.40 m (Ph, =CHBr). Found,
%: C 47.9; H 3.1; Cl 7.1; Pt 19.5. C40H32Br2Cl2P2Pt.
Calculated, %: C 48.0; H 3.2; Cl 7.1; Pt 19.5.
(0.313), 1588 (0.345), 1595 (0.362), 3000 (0.219),
trans-Dichlorobis[(2-bromo-1-phenylvinyl)di-
phenylphosphine]platinum(II) was prepared simi-
larly from 53.3 mg of (2-bromo-1-phenylvinyl)di-
phenylphosphine and 34.1 mg of dichlorobis(dimethyl
sulfoxide)platinum(II). Yield 25.3 mg (31%), mp
1
3027 (0.200), 3067 (0.183). H NMR spectrum,
,
3
ppm: 6.02 d (1H, CH=, JHP 11.4 Hz), 7.27 7.64 m
(15H, Ph). 5.29 ppm.
P
Tris(Z-styryl)phosphine [9, 10]. IR spectrum,
,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 5 2005

696
REZNIKOV et al.
1
191 C. IR spectrum (KBr), , cm : 460 (0.220), 590
(0.310), 610 (0.300), 685 (0.500), 740 (0.670), 762
(0.714), 898 (0.700), 930 (0.655), 995 (0.608), 1025
under argon to a boiling solution of 1.632 g of tris(Z-
styryl)phosphine in 20 ml of ethanol. The precipitate
of the complex thus formed was filtered off, washed
with ethanol and diethyl ether, and dried. Yield
(0.582), 1095 (0.479), 1425 (0.332), 1470 (0.330),
1605 (0.132), 1625 (0.160). H NMR spectrum,
1
1
,
1.271 g (63%), mp 166 C. IR spectrum, , cm : 530
ppm: 6.95 7.85 m (Ph, CHBr). Found, %: C 47.8; H (0.708), 596 (0.838), 615 (0.847), 656 (0.830), 695
3.1, Cl 7.2, Pt 19.4. C40H32Br2Cl2P2Pt. Calculated,%:
C 48.0; H 3.2; Cl 7.1; Pt 19.5.
(0.557), 723 (0.783), 741 (0.780), 774 (0.540), 835
(0.896), 853 (0.870), 920 (0.869), 970 (0.893), 1027
(0.889), 1074 (0.873), 1178 (0.908), 1225 (0.929),
1318 (0.928), 1372 (0.940), 1443 (0.773), 1490
(0.774), 1572 (0.795), 1590 (0.741), 2921 (0.940),
trans-Dichlorobis[(2-bromo-1-phenylvinyl)di-
phenylphosphine]palladium(II).
A
solution of
395 mg of (2-bromo-1-phenylvinyl)diphenylphos-
phine in 5 ml of methylene chloride was added in
small portions under argon to a solution of 193 mg of
dichlorobis(benzonitrile)palladium(II) in 5 ml of
methylene chloride. The mixture was left overnight.
The solvent was partially distilled off, and the residue
was poured into 30 ml of hexane. The precipitate thus
formed was filtered off, washed with diethyl ether,
and dried. Yield 176 mg (38%), mp 182 C. IR spec-
1
3021 (0.802), 3052 (0.882), 3438 (0.836). H NMR
spectrum, , ppm: 6.26 m (1H, CH=), 6.82 m (1H,
CH=), 7.14 7.34 m (5H, Ph). Found, %: C 67.2; H
5.0; Cl 8.3; Pd 12.4. C48H42Cl2P2Pd. Calculated, %:
C 67.2; H 4.9; Cl 8.3; Pd 12.4.
ACKNOWLEDGMENTS
The study was financially supported by the Russian
Foundation for Basic Research (project no. 04-03-
32632a).
1
trum (KBr), , cm : 461 (0.816), 502 (0.693), 533
(0.874), 558 (0.801), 592 (0.832), 691 (0.585), 745
(0.765), 766 (0.862), 809 (0.931), 816 (0.927), 901
(0.892), 935 (0.880), 999 (0.894), 1028 (0.882), 1071
(0.887), 1093 (0.806), 1154 (0.935), 1186 (0.911),
1276 (0.898), 1310 (0.910), 1434 (0.677), 1480
(0.847), 1487 (0.846), 1561 (0.844), 1578 (0.830),
3051 (0.889). 1H NMR spectrum, , ppm: 6.90
7.75 m (Ph, CHBr=). Found, %: C 52.6; H 3.6; Cl
7.7; Pd 11.7. C40H32Br2Cl2P2Pd. Calculated, %: C
52.7; H 3.5; Cl 7.8; Pd 11.7.
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New York: Plenum, 1984.
trans-Dichlorobis[tris(Z-styryl)phosphine]pla-
tinum(II). A solution of 183 mg of tris(Z-styryl)-
phosphine in 5 ml of ethanol was added dropwise
with stirring under argon over a period of 1 h to a
saturated solution of 99.2 mg of potassium tetrachlo-
roplatinate(IV). The precipitate thus formed was
filtered off, washed with ethanol and diethyl ether,
and dried. Yield 101 mg (45%), mp 171 C. IR spec-
1
trum (KBr), , cm : 529 (0.678), 598 (0.861), 615
(0.888), 655 (0.849), 692 (0.648), 702 (0.688), 741
(0.778), 777 (0.609), 852 (0.901), 917 (0.905), 1027
(0.912), 1073 (0.905), 1156 (0.928), 1179 (0.933),
1229 (0.949), 1320 (0.949), 1364 (0.952), 1399
(0.944), 1444 (0.829), 1491 (0.814), 1572 (0.831),
1593 (0.798), 2925 (0.906), 2996 (0.884), 3023
1
(0.844), 3051 (0.846), 3438 (0.708). H NMR spec-
trum, , ppm: 6.29 m (1H, CH=), 6.86 m (1H, CH=),
7.19 7.43 m (5H, Ph). Found, %: C 60.9; H 4.4; Cl
7.5; Pt 20.6. C48H42Cl2P2Pt. Calculated, %: C 60.9; H
4.5; Cl 7.5; Pt 20.6.
trans-Dichlorobis[tris(Z-styryl)phosphine]pal-
ladium(II). A solution of 0.420 g of palladium chlo-
ride in 11 ml of concentrated hydrochloric acid and
11 ml of water was added dropwise with stirring
13. Fontaine, X.L.R., Markham, D.P., and Shaw, B.L.,
J. Organomet. Chem., 1990, vol. 391, no. 1, p. 123.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 5 2005