trans-1,3-pentadiene and cyclobutene complexes of rhodium(I) and iridium(I)

Robert B. Osborne; James A. Ibers

doi:10.1016/S0022-328X(82)80021-1

trans-1,3-pentadiene and cyclobutene complexes of rhodium(I) and iridium(I)

Robert B. Osborne^*, James A. Ibers

^*Corresponding author for this work

Chemistry

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

Abstract

The generation of “MClL₂” centers in THF solution (M = Ir, L = AsPh₃, SbPh₃; M = Rh, L = SbPh₃) leads to stable η²-MCl(C₅H₈)L₂ complexes on the addition of an excess of trans-1,3-pentadiene. For IrCl(PPh₃)₂, it is only possible to recover a clean pentadiene complex if the reaction is carried out in neat diene solution. Cyclobutene also coordinates to “IrClL₂” (L = AsPh₃, SbPh₃) to form an IrCl(C₄H₆)L₂ product when excess cyclobutene is condensed with a starting material at −78°C, THF is added, and the solution is warmed to 25°C. These 16-electron MCl(olefin)L₂ complexes are stable to disproportionation after isolation from solution. The most stable complexes are formed with the tertiary arsine and stibine ligands for M = Ir.

Original language	English (US)
Pages (from-to)	267-272
Number of pages	6
Journal	Journal of Organometallic Chemistry
Volume	232
Issue number	1
DOIs	https://doi.org/10.1016/S0022-328X(82)80021-1
State	Published - Jan 1 1982

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/S0022-328X(82)80021-1

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title = "trans-1,3-pentadiene and cyclobutene complexes of rhodium(I) and iridium(I)",

abstract = "The generation of “MClL2” centers in THF solution (M = Ir, L = AsPh3, SbPh3; M = Rh, L = SbPh3) leads to stable η2-MCl(C5H8)L2 complexes on the addition of an excess of trans-1,3-pentadiene. For IrCl(PPh3)2, it is only possible to recover a clean pentadiene complex if the reaction is carried out in neat diene solution. Cyclobutene also coordinates to “IrClL2” (L = AsPh3, SbPh3) to form an IrCl(C4H6)L2 product when excess cyclobutene is condensed with a starting material at −78°C, THF is added, and the solution is warmed to 25°C. These 16-electron MCl(olefin)L2 complexes are stable to disproportionation after isolation from solution. The most stable complexes are formed with the tertiary arsine and stibine ligands for M = Ir.",

author = "Osborne, {Robert B.} and Ibers, {James A.}",

year = "1982",

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doi = "10.1016/S0022-328X(82)80021-1",

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TY - JOUR

T1 - trans-1,3-pentadiene and cyclobutene complexes of rhodium(I) and iridium(I)

AU - Osborne, Robert B.

AU - Ibers, James A.

PY - 1982/1/1

Y1 - 1982/1/1

N2 - The generation of “MClL2” centers in THF solution (M = Ir, L = AsPh3, SbPh3; M = Rh, L = SbPh3) leads to stable η2-MCl(C5H8)L2 complexes on the addition of an excess of trans-1,3-pentadiene. For IrCl(PPh3)2, it is only possible to recover a clean pentadiene complex if the reaction is carried out in neat diene solution. Cyclobutene also coordinates to “IrClL2” (L = AsPh3, SbPh3) to form an IrCl(C4H6)L2 product when excess cyclobutene is condensed with a starting material at −78°C, THF is added, and the solution is warmed to 25°C. These 16-electron MCl(olefin)L2 complexes are stable to disproportionation after isolation from solution. The most stable complexes are formed with the tertiary arsine and stibine ligands for M = Ir.

AB - The generation of “MClL2” centers in THF solution (M = Ir, L = AsPh3, SbPh3; M = Rh, L = SbPh3) leads to stable η2-MCl(C5H8)L2 complexes on the addition of an excess of trans-1,3-pentadiene. For IrCl(PPh3)2, it is only possible to recover a clean pentadiene complex if the reaction is carried out in neat diene solution. Cyclobutene also coordinates to “IrClL2” (L = AsPh3, SbPh3) to form an IrCl(C4H6)L2 product when excess cyclobutene is condensed with a starting material at −78°C, THF is added, and the solution is warmed to 25°C. These 16-electron MCl(olefin)L2 complexes are stable to disproportionation after isolation from solution. The most stable complexes are formed with the tertiary arsine and stibine ligands for M = Ir.

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U2 - 10.1016/S0022-328X(82)80021-1

DO - 10.1016/S0022-328X(82)80021-1

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VL - 232

SP - 267

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JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1

ER -

trans-1,3-pentadiene and cyclobutene complexes of rhodium(I) and iridium(I)

Abstract

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