η6-tetramethylfulvene and μ-η3: η3-benzene complexes of iridium

Joseph M. Meredith; Karen I. Goldberg; Werner Kaminsky; D. Michael Heinekey

doi:10.1021/om3010492

η⁶-tetramethylfulvene and μ-η³: η³-benzene complexes of iridium

Joseph M. Meredith, Karen I. Goldberg, Werner Kaminsky, D. Michael Heinekey

Chemistry Department

University of Washington

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

17 Scopus citations

Abstract

The reaction of Cp*Ir(NHC)Me₂ (Ir-Me₂) with [CPh₃]⁺[B(C₆F₅)₄] ^- in dichloromethane resulted in conversion of the Cp* ligand to an η⁶-tetramethylfulvene ligand via apparent hydride abstraction (Cp* = η⁵-C₅Me₅; NHC = 1,3-N,N-dimethylimidazol-2-ylidene). The products of this reaction are triphenylmethane and the η⁶-tetramethylfulvene complex [(η⁶-C₅Me₄=CH₂)Ir(NHC)(Me ₂)]⁺[B(C₆F₅)₄] ^- (fulv-Ir⁺). When dichloromethane solutions of the related complex [Cp*Ir(NHC)(Ph)(solv)]⁺[MeB(C₆F ₅)₃]^- were allowed to stand at room temperature, crystals of the unusual sandwich complex [{Cp*Ir(NHC)} ₂(μ-η³:η³-C₆H ₆)]²⁺ (Ir-C₆H₆-Ir²⁺) were obtained. Complexes fulv-Ir⁺ and Ir-C₆H ₆-Ir²⁺ represent unique architectures in the Cp*Ir(NHC) family. Both compounds were characterized by spectroscopic methods as well as by single-crystal X-ray diffraction.

Original language	English
Pages (from-to)	8459-8462
Number of pages	4
Journal	Organometallics
Volume	31
Issue number	23
DOIs	https://doi.org/10.1021/om3010492
State	Published - 10 Dec 2012

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@article{15fb6a76dd76438bb461e224eb23c204,

title = "η6-tetramethylfulvene and μ-η3: η3-benzene complexes of iridium",

abstract = "The reaction of Cp*Ir(NHC)Me2 (Ir-Me2) with [CPh3]+[B(C6F5)4] - in dichloromethane resulted in conversion of the Cp* ligand to an η6-tetramethylfulvene ligand via apparent hydride abstraction (Cp* = η5-C5Me5; NHC = 1,3-N,N-dimethylimidazol-2-ylidene). The products of this reaction are triphenylmethane and the η6-tetramethylfulvene complex [(η6-C5Me4=CH2)Ir(NHC)(Me 2)]+[B(C6F5)4] - (fulv-Ir+). When dichloromethane solutions of the related complex [Cp*Ir(NHC)(Ph)(solv)]+[MeB(C6F 5)3]- were allowed to stand at room temperature, crystals of the unusual sandwich complex [{Cp*Ir(NHC)} 2(μ-η3:η3-C6H 6)]2+ (Ir-C6H6-Ir2+) were obtained. Complexes fulv-Ir+ and Ir-C6H 6-Ir2+ represent unique architectures in the Cp*Ir(NHC) family. Both compounds were characterized by spectroscopic methods as well as by single-crystal X-ray diffraction.",

author = "Meredith, {Joseph M.} and Goldberg, {Karen I.} and Werner Kaminsky and Heinekey, {D. Michael}",

year = "2012",

month = dec,

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doi = "10.1021/om3010492",

language = "English",

volume = "31",

pages = "8459--8462",

number = "23",

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T1 - η6-tetramethylfulvene and μ-η3

T2 - η3-benzene complexes of iridium

AU - Meredith, Joseph M.

AU - Goldberg, Karen I.

AU - Kaminsky, Werner

AU - Heinekey, D. Michael

PY - 2012/12/10

Y1 - 2012/12/10

N2 - The reaction of Cp*Ir(NHC)Me2 (Ir-Me2) with [CPh3]+[B(C6F5)4] - in dichloromethane resulted in conversion of the Cp* ligand to an η6-tetramethylfulvene ligand via apparent hydride abstraction (Cp* = η5-C5Me5; NHC = 1,3-N,N-dimethylimidazol-2-ylidene). The products of this reaction are triphenylmethane and the η6-tetramethylfulvene complex [(η6-C5Me4=CH2)Ir(NHC)(Me 2)]+[B(C6F5)4] - (fulv-Ir+). When dichloromethane solutions of the related complex [Cp*Ir(NHC)(Ph)(solv)]+[MeB(C6F 5)3]- were allowed to stand at room temperature, crystals of the unusual sandwich complex [{Cp*Ir(NHC)} 2(μ-η3:η3-C6H 6)]2+ (Ir-C6H6-Ir2+) were obtained. Complexes fulv-Ir+ and Ir-C6H 6-Ir2+ represent unique architectures in the Cp*Ir(NHC) family. Both compounds were characterized by spectroscopic methods as well as by single-crystal X-ray diffraction.

AB - The reaction of Cp*Ir(NHC)Me2 (Ir-Me2) with [CPh3]+[B(C6F5)4] - in dichloromethane resulted in conversion of the Cp* ligand to an η6-tetramethylfulvene ligand via apparent hydride abstraction (Cp* = η5-C5Me5; NHC = 1,3-N,N-dimethylimidazol-2-ylidene). The products of this reaction are triphenylmethane and the η6-tetramethylfulvene complex [(η6-C5Me4=CH2)Ir(NHC)(Me 2)]+[B(C6F5)4] - (fulv-Ir+). When dichloromethane solutions of the related complex [Cp*Ir(NHC)(Ph)(solv)]+[MeB(C6F 5)3]- were allowed to stand at room temperature, crystals of the unusual sandwich complex [{Cp*Ir(NHC)} 2(μ-η3:η3-C6H 6)]2+ (Ir-C6H6-Ir2+) were obtained. Complexes fulv-Ir+ and Ir-C6H 6-Ir2+ represent unique architectures in the Cp*Ir(NHC) family. Both compounds were characterized by spectroscopic methods as well as by single-crystal X-ray diffraction.

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U2 - 10.1021/om3010492

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JO - Organometallics

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ER -

η⁶-tetramethylfulvene and μ-η³: η³-benzene complexes of iridium

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