C–C Bond Cleavage in Hydrocarbons by Iridium Complexes

Robert H. Crabtree; Robert P. Dion; David J. Gibboni; Dominic V. McGrath; Elizabeth M. Holt

doi:10.1021/ja00283a015

C–C Bond Cleavage in Hydrocarbons by Iridium Complexes

Robert H. Crabtree, Robert P. Dion, David J. Gibboni, Dominic V. McGrath, Elizabeth M. Holt

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

130 Scopus citations

Abstract

A variety of transformations involving C-C bond cleavage in iridium complexes is described. 1,1-Dimethylcyclopentane reacts with [IrH2(Me2CO)₂L₂]SbF₆ (L = (p-FC₆H₄)₃P, 1) to give first [(5,5-C₅H₄Me₂)IrL₂]SbF₆(2) and then [(MeC₅H₄)lrMeL₂]SbF₆ (3). The corresponding 5,5-dimethylcyclopentadiene gives 1,2- and 1,3-diethylcvclopentadienyl complexes by a route that involves alkyl migration from ring to metal and back. 4,4-Dimethylcyclopentene also reacts to give 3 but the 3,3-isomer follows a different path to give [(MeC₅H4)IrHL₂]SbF₆. Crystal structures of two diene complexes of type 2 are reported and mechanisms for the reactions observed are proposed.

Original language	English (US)
Pages (from-to)	7222-7227
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	108
Issue number	23
DOIs	https://doi.org/10.1021/ja00283a015
State	Published - 1986
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "C–C Bond Cleavage in Hydrocarbons by Iridium Complexes",

abstract = "A variety of transformations involving C-C bond cleavage in iridium complexes is described. 1,1-Dimethylcyclopentane reacts with [IrH2(Me2CO)2L2]SbF6 (L = (p-FC6H4)3P, 1) to give first [(5,5-C5H4Me2)IrL2]SbF6(2) and then [(MeC5H4)lrMeL2]SbF6 (3). The corresponding 5,5-dimethylcyclopentadiene gives 1,2- and 1,3-diethylcvclopentadienyl complexes by a route that involves alkyl migration from ring to metal and back. 4,4-Dimethylcyclopentene also reacts to give 3 but the 3,3-isomer follows a different path to give [(MeC5H4)IrHL2]SbF6. Crystal structures of two diene complexes of type 2 are reported and mechanisms for the reactions observed are proposed.",

author = "Crabtree, {Robert H.} and Dion, {Robert P.} and Gibboni, {David J.} and McGrath, {Dominic V.} and Holt, {Elizabeth M.}",

year = "1986",

doi = "10.1021/ja00283a015",

language = "English (US)",

volume = "108",

pages = "7222--7227",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "23",

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TY - JOUR

T1 - C–C Bond Cleavage in Hydrocarbons by Iridium Complexes

AU - Crabtree, Robert H.

AU - Dion, Robert P.

AU - Gibboni, David J.

AU - McGrath, Dominic V.

AU - Holt, Elizabeth M.

PY - 1986

Y1 - 1986

N2 - A variety of transformations involving C-C bond cleavage in iridium complexes is described. 1,1-Dimethylcyclopentane reacts with [IrH2(Me2CO)2L2]SbF6 (L = (p-FC6H4)3P, 1) to give first [(5,5-C5H4Me2)IrL2]SbF6(2) and then [(MeC5H4)lrMeL2]SbF6 (3). The corresponding 5,5-dimethylcyclopentadiene gives 1,2- and 1,3-diethylcvclopentadienyl complexes by a route that involves alkyl migration from ring to metal and back. 4,4-Dimethylcyclopentene also reacts to give 3 but the 3,3-isomer follows a different path to give [(MeC5H4)IrHL2]SbF6. Crystal structures of two diene complexes of type 2 are reported and mechanisms for the reactions observed are proposed.

AB - A variety of transformations involving C-C bond cleavage in iridium complexes is described. 1,1-Dimethylcyclopentane reacts with [IrH2(Me2CO)2L2]SbF6 (L = (p-FC6H4)3P, 1) to give first [(5,5-C5H4Me2)IrL2]SbF6(2) and then [(MeC5H4)lrMeL2]SbF6 (3). The corresponding 5,5-dimethylcyclopentadiene gives 1,2- and 1,3-diethylcvclopentadienyl complexes by a route that involves alkyl migration from ring to metal and back. 4,4-Dimethylcyclopentene also reacts to give 3 but the 3,3-isomer follows a different path to give [(MeC5H4)IrHL2]SbF6. Crystal structures of two diene complexes of type 2 are reported and mechanisms for the reactions observed are proposed.

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DO - 10.1021/ja00283a015

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 23

ER -

C–C Bond Cleavage in Hydrocarbons by Iridium Complexes

Abstract

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