Bis tricyclohexylphosphine platinum

K2PtCl4 + 2P(cyclo-C6H u)3 - fram-PtCl2[P(cyc7o-C6Hu)3] 2 + 2KC1 

KzCPtClJ -I- 2P(cyc/o-C6Hii)3- trans-PtCl2[P(cydo-QHii)3]2 -I- 2KC1 rrans-PtCl2[P(cyc/o-C5Hii)3]2 -I- 2[CioHg]Na -  

The filtrate is concentrated in vacuo and the resulting solid is heated at 50-70° in vacuo (10 torr) for 10 hours to ranove the naphthalene by sublimation. It is then dissolved in hot hexane (30 mL) and the solution is filtered as above. Concentration of the filtrate in vacuo to 5 mL gives pale-yellow crystals. After standing in a freezer (—35°) overnight, the crystals (0.40 g) are isolated by removing the mother liquor with a syringe, washed with hexane (three 2-mL portions), and dried in vacuo. Additional crystals (0.10 g) are obtained on concentration of the combined mother liquor and washings to 1 mL. Total yield 55%.t Colorless crystals are obtained by recrystallization from hexane mp 204-208° (under N2 sealed capfllary tube). 

The bicoordinate complexes described here are soluble in benzene and hexane. The Pd[P(t-Bu)3]2 complex is stable in air in the solid state, whereas 

Shriver, The Manipulation Air-Sensitive Compounds, M raw-Hill, New York, 1969. 

Tatsuno, T. Yoshida, and S. Otsuka, Inorg. Synth., 19,220(1979) also see section 88 in this volume. 

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Many years ago, Fomies showed that bis-tricyclohexylphosphine platinum(O) reacts with substrates that contain acidic X-H bonds, such as pentafluoroaniline, and Otsuka showed that platinum(O) and palladium(O) complexes containing hindered trialkyl and mixed alkyl aryl phosphine ligands react with acidic substrates, such as carboxylic acids (Equation 7.16), to form products of oxidative addition. ... 

CftsHysFsPaPt, (T -Ally1)bis(tricyclohexylphosphine)platinum hexafluorophosphate - toluene, 44B, 754 Ci,7H39CoCr05P3S2 0.25 CH2Cl2r [l,lrl-Tris(diphenylphosphinometh-yl)ethane]cobalt(M"carbon disulfide)pentacarbonylehromiurn methylene chloride, 46B, 857... 

C3 gHs sP2Pt, Bis(tricyclohexylphosphine)platinum(O), 4IB, 1202 C3sH7oP2PtSi, trans Hydridosilyl(tricyclohexylphosphineiplatinum-dl), 44B, 1073... 

Significant advances in organonickel chemistry followed the discovery of frtzws,fraws,fraws-(l,5,9-cyclododecatriene)nickel, Ni(cdt), and bis(l,5-cycloocta-diene)nickel Ni(cod)2 by Wilke et. al.1 In these and related compounds, in which only olefinic ligands are bonded to the nickel, the metal is especially reactive both in the synthesis of other compounds and in catalytic behavior. Extension of this chemistry to palladium and to platinum has hitherto been inhibited by the lack of convenient synthetic routes to zero-valent complexes of these metals in which mono- or diolefins are the only ligands. Here we described the synthesis of bis(l,5-cyclooctadiene)platinum, tris(ethylene)-platinum, and bis(ethylene)(tricyclohexylphosphine)platinum. The compound Pt(cod)2 (cod = 1,5-cyclooctadiene) was first reported by Muller and Goser,2 who prepared it by the following reaction sequence ... 

Braunschweig H, Damme A. Thermodynamic control of oxidative addition and reductive elimination processes in us-bis(dimethoxyhoryl)-his(tricyclohexylphosphine)-platinum(II). Chem Commun. 2013 49 5216-5218. 

The apparatus is flushed with ethene until the solvent is saturated. Bis(l,S-cyclooctadiene)platinum (3.8 g, 9.2 mmol) is added in small (0.2-g) portions, and each portion is allowed to dissolve before the next is added. A petroleum ether solution of tricyclohexylphosphine (2.6 g, 9.2 mmol in IS mL) is added slowly. After a brief evolution of gas, crystallization of the product begins. The ethene source is removed, and the flask is flushed with a slow stream of nitrogen for 1 h. The supernatant liquid is decanted into a clean flask, and the crystals are washed well with cold petroleum ether (four 10-mL portions) the washings are added to the mother liquor. The white crystals may be dried at 20°C (0.05 torr) for 1 h. 

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