Reactions of Nickel, Palladium, and Platinum Complexes with Carbonyl Sulfide

Thomas R. Gaffney; James A Ibers

doi:10.1021/ic00137a064

Reactions of Nickel, Palladium, and Platinum Complexes with Carbonyl Sulfide

Thomas R. Gaffney, James A Ibers^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

36 Scopus citations

Abstract

The complexes ML₃ (M = Ni, Pd, Pt; L = PPh₃, P(p-C₆H₄CH₃)₃) react with carbonyl sulfide to afford M(CO)L₃, M(CO)₂L₂, M(η²-COS)L₂, and M(COS₂)L₂ complexes, depending upon M, L, and reaction conditions. These reactions are contrasted with those involving CS₂ in place of COS. A mechanism for the reductive disproportionation of COS by Pt(PPh₃)₄ involving a metal-sulfide intermediate is proposed. The dioxygen complexes Pt(O₂)L₂ and Pd(O₂)L₂ react with carbonyl sulfide to afford metal thiocarbonates, Pt(CO₂S)L₂ and Pd(CO₂S)L₂, in which the thiocarbonate ligand is asymmetrically bound to the metal.

Original language	English (US)
Pages (from-to)	2860-2864
Number of pages	5
Journal	Inorganic Chemistry
Volume	21
Issue number	7
DOIs	https://doi.org/10.1021/ic00137a064
State	Published - Jan 1 1982

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Reactions of Nickel, Palladium, and Platinum Complexes with Carbonyl Sulfide",

abstract = "The complexes ML3 (M = Ni, Pd, Pt; L = PPh3, P(p-C6H4CH3)3) react with carbonyl sulfide to afford M(CO)L3, M(CO)2L2, M(η2-COS)L2, and M(COS2)L2 complexes, depending upon M, L, and reaction conditions. These reactions are contrasted with those involving CS2 in place of COS. A mechanism for the reductive disproportionation of COS by Pt(PPh3)4 involving a metal-sulfide intermediate is proposed. The dioxygen complexes Pt(O2)L2 and Pd(O2)L2 react with carbonyl sulfide to afford metal thiocarbonates, Pt(CO2S)L2 and Pd(CO2S)L2, in which the thiocarbonate ligand is asymmetrically bound to the metal.",

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TY - JOUR

T1 - Reactions of Nickel, Palladium, and Platinum Complexes with Carbonyl Sulfide

AU - Gaffney, Thomas R.

AU - Ibers, James A

PY - 1982/1/1

Y1 - 1982/1/1

N2 - The complexes ML3 (M = Ni, Pd, Pt; L = PPh3, P(p-C6H4CH3)3) react with carbonyl sulfide to afford M(CO)L3, M(CO)2L2, M(η2-COS)L2, and M(COS2)L2 complexes, depending upon M, L, and reaction conditions. These reactions are contrasted with those involving CS2 in place of COS. A mechanism for the reductive disproportionation of COS by Pt(PPh3)4 involving a metal-sulfide intermediate is proposed. The dioxygen complexes Pt(O2)L2 and Pd(O2)L2 react with carbonyl sulfide to afford metal thiocarbonates, Pt(CO2S)L2 and Pd(CO2S)L2, in which the thiocarbonate ligand is asymmetrically bound to the metal.

AB - The complexes ML3 (M = Ni, Pd, Pt; L = PPh3, P(p-C6H4CH3)3) react with carbonyl sulfide to afford M(CO)L3, M(CO)2L2, M(η2-COS)L2, and M(COS2)L2 complexes, depending upon M, L, and reaction conditions. These reactions are contrasted with those involving CS2 in place of COS. A mechanism for the reductive disproportionation of COS by Pt(PPh3)4 involving a metal-sulfide intermediate is proposed. The dioxygen complexes Pt(O2)L2 and Pd(O2)L2 react with carbonyl sulfide to afford metal thiocarbonates, Pt(CO2S)L2 and Pd(CO2S)L2, in which the thiocarbonate ligand is asymmetrically bound to the metal.

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Reactions of Nickel, Palladium, and Platinum Complexes with Carbonyl Sulfide

Abstract

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