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• W1988926215 abstract "Anion redistribution equilibria of the type (R3P)2MX2 + (R3P)2MY2 ⇆ 2(R3P)2 MXY (X, Y = Cl, Br, I, CN, N3; R3P = Me2PhP, MePh2P, (Bzl)3P, (CH2CH)2PhP, (CH2CH)Ph2P and 1-phenyl-3,4-dimethylphosphole; M = Pd, Pt) have been studied by 31P{1H} and in some cases 195Pt{1H} NMR spectroscopy. It was found that except for the two cases when R3P = MePh2P, M = Pd, X = Cl, Y = Br and R3P = Me2PhP, M = Pd, X = Cl, Y = Br, redistribution was in general instantaneous. The (R3P)2PdCl2+ (R3P)2Pd(CN)2 reactions were slow but proceeded to completion. In contrast, when one of the anions is CN− no anion redistribution was observed for the platinum complexes even after a month. The thermodynamic stabilities of the mixed anion species relative to the symmetric species is anion dependent showing that these are not random processes. The (R3P)2PdXY complexes possess the trans geometry. The (R3P)2PtXY complexes are generally cis but in some cases both the cis and trans isomers are present in solution. A mechanism is proposed for these reactions. Phosphine redistribution of the type (R3P)2MX2+(R′3P)2MX2 ⇇ 2(R3P)(R′3P)2MX2 is general for palladium. It did not occur for platinum unless one or more of the R and R′ groups on each phosphine was unsaturated (allyl, vinyl or the butadiene moiety of a phosphole). In most of these cases the (R3P)(R′3P)MX2 complexes underwent intramolecular [4+2] Diels-Alder cycloaddition reactions." @default.
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• W1988926215 date "1989-01-01" @default.
• W1988926215 modified "2023-10-16" @default.
• W1988926215 title "Redistribution reactions of platinum(II) and palladium(II) phosphine complexes" @default.
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• W1988926215 doi "https://doi.org/10.1016/s0277-5387(00)86441-4" @default.
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