Formal Insertion of Sulfur into a Metal-Hydride Bond: Formation of Rh(SH)(CO)(P(C6H5)3)2 from RhH(P(C6H5)3)4 and COS

Thomas R. Gaffney; James A Ibers

doi:10.1021/ic00137a063

Formal Insertion of Sulfur into a Metal-Hydride Bond: Formation of Rh(SH)(CO)(P(C₆H₅)₃)₂ from RhH(P(C₆H₅)₃)₄ and COS

Thomas R. Gaffney, James A Ibers^*

^*Corresponding author for this work

Chemistry

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

33 Scopus citations

Abstract

The reaction of RhH(PPh₃)₄ with carbonyl sulfide affords trans-mercaptocarbonylbis(triphenylphosphine)rhodium(I), Rh(SH)(CO)(PPh₃)₂, in high yield. The product has been characterized by infrared, ¹H, and ³¹P{¹H} NMR spectroscopy and by an X-ray structure determination. A pathway to the formation of the compound is proposed that involves η² coordination of the COS molecule to the metal center, with subsequent hydride transfer to the sulfur atom and C—S bond cleavage.

Original language	English (US)
Pages (from-to)	2857-2859
Number of pages	3
Journal	Inorganic Chemistry
Volume	21
Issue number	7
DOIs	https://doi.org/10.1021/ic00137a063
State	Published - Jan 1 1982

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Formal Insertion of Sulfur into a Metal-Hydride Bond: Formation of Rh(SH)(CO)(P(C6H5)3)2 from RhH(P(C6H5)3)4 and COS",

abstract = "The reaction of RhH(PPh3)4 with carbonyl sulfide affords trans-mercaptocarbonylbis(triphenylphosphine)rhodium(I), Rh(SH)(CO)(PPh3)2, in high yield. The product has been characterized by infrared, 1H, and 31P{1H} NMR spectroscopy and by an X-ray structure determination. A pathway to the formation of the compound is proposed that involves η2 coordination of the COS molecule to the metal center, with subsequent hydride transfer to the sulfur atom and C—S bond cleavage.",

author = "Gaffney, {Thomas R.} and Ibers, {James A}",

year = "1982",

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doi = "10.1021/ic00137a063",

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T1 - Formal Insertion of Sulfur into a Metal-Hydride Bond

T2 - Formation of Rh(SH)(CO)(P(C6H5)3)2 from RhH(P(C6H5)3)4 and COS

AU - Gaffney, Thomas R.

AU - Ibers, James A

PY - 1982/1/1

Y1 - 1982/1/1

N2 - The reaction of RhH(PPh3)4 with carbonyl sulfide affords trans-mercaptocarbonylbis(triphenylphosphine)rhodium(I), Rh(SH)(CO)(PPh3)2, in high yield. The product has been characterized by infrared, 1H, and 31P{1H} NMR spectroscopy and by an X-ray structure determination. A pathway to the formation of the compound is proposed that involves η2 coordination of the COS molecule to the metal center, with subsequent hydride transfer to the sulfur atom and C—S bond cleavage.

AB - The reaction of RhH(PPh3)4 with carbonyl sulfide affords trans-mercaptocarbonylbis(triphenylphosphine)rhodium(I), Rh(SH)(CO)(PPh3)2, in high yield. The product has been characterized by infrared, 1H, and 31P{1H} NMR spectroscopy and by an X-ray structure determination. A pathway to the formation of the compound is proposed that involves η2 coordination of the COS molecule to the metal center, with subsequent hydride transfer to the sulfur atom and C—S bond cleavage.

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JF - Inorganic Chemistry

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Formal Insertion of Sulfur into a Metal-Hydride Bond: Formation of Rh(SH)(CO)(P(C₆H₅)₃)₂ from RhH(P(C₆H₅)₃)₄ and COS

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