Geometrically Distorted and Redox-Active Organometallic Iridium Complexes Containing Biphenyl-2,2'-diyl

Zheng Lu; Chul Ho Jun; Susan R. de Gala; Robert H. Crabtree; Michael P. Sigalas; Odile Eisenstein

doi:10.1021/om00003a018

Geometrically Distorted and Redox-Active Organometallic Iridium Complexes Containing Biphenyl-2,2'-diyl

Zheng Lu, Chul Ho Jun, Susan R. de Gala, Robert H. Crabtree, Michael P. Sigalas, Odile Eisenstein

Department of Chemistry

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

74 Citations (Scopus)

Abstract

C-C bond cleavage of biphenylene by an Ir(I) complex via an oxidation addition generates the biph (=biphenyl-2,2^'-diyl) ligand. The resulting compound is treated with PPh₃ to give [Ir(PPh₃)₂(biph)Cl], having a 16 e five-coordinate structure lying between Y and T geometries, being closer to a Y, which is rationalized on theoretical grounds. The complex [Ir(PMe₃)₃-(biph)Cl] can be oxidized quasi-reversibly to an Ir(IV) species. Oxidation with NOEF₄ gives the unusual Ir(IV) boryl compound [Ir(PMe₃)₃(biphBF)Cl]⁺, which has been isolated and structurally characterized. Extended Hückel (EHT) calculations suggest that the easy oxidation of the (Ir(biph)} system is associated with the presence of a high-lying Ir d_yz orbital. The (Ir(biph)} fragment is remarkably stable; only Br₂ is able to cleave the Ir-C bonds.

Original language	English
Pages (from-to)	1168-1175
Number of pages	8
Journal	Organometallics
Volume	14
Issue number	3
DOIs	https://doi.org/10.1021/om00003a018
Publication status	Published - 1995 Mar

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om00003a018

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title = "Geometrically Distorted and Redox-Active Organometallic Iridium Complexes Containing Biphenyl-2,2'-diyl",

abstract = "C-C bond cleavage of biphenylene by an Ir(I) complex via an oxidation addition generates the biph (=biphenyl-2,2'-diyl) ligand. The resulting compound is treated with PPh3 to give [Ir(PPh3)2(biph)Cl], having a 16 e five-coordinate structure lying between Y and T geometries, being closer to a Y, which is rationalized on theoretical grounds. The complex [Ir(PMe3)3-(biph)Cl] can be oxidized quasi-reversibly to an Ir(IV) species. Oxidation with NOEF4 gives the unusual Ir(IV) boryl compound [Ir(PMe3)3(biphBF)Cl]+, which has been isolated and structurally characterized. Extended H{\"u}ckel (EHT) calculations suggest that the easy oxidation of the (Ir(biph)} system is associated with the presence of a high-lying Ir dyz orbital. The (Ir(biph)} fragment is remarkably stable; only Br2 is able to cleave the Ir-C bonds.",

author = "Zheng Lu and Jun, {Chul Ho} and {de Gala}, {Susan R.} and Crabtree, {Robert H.} and Sigalas, {Michael P.} and Odile Eisenstein",

year = "1995",

month = mar,

doi = "10.1021/om00003a018",

language = "English",

volume = "14",

pages = "1168--1175",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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T1 - Geometrically Distorted and Redox-Active Organometallic Iridium Complexes Containing Biphenyl-2,2'-diyl

AU - Lu, Zheng

AU - Jun, Chul Ho

AU - de Gala, Susan R.

AU - Crabtree, Robert H.

AU - Sigalas, Michael P.

AU - Eisenstein, Odile

PY - 1995/3

Y1 - 1995/3

N2 - C-C bond cleavage of biphenylene by an Ir(I) complex via an oxidation addition generates the biph (=biphenyl-2,2'-diyl) ligand. The resulting compound is treated with PPh3 to give [Ir(PPh3)2(biph)Cl], having a 16 e five-coordinate structure lying between Y and T geometries, being closer to a Y, which is rationalized on theoretical grounds. The complex [Ir(PMe3)3-(biph)Cl] can be oxidized quasi-reversibly to an Ir(IV) species. Oxidation with NOEF4 gives the unusual Ir(IV) boryl compound [Ir(PMe3)3(biphBF)Cl]+, which has been isolated and structurally characterized. Extended Hückel (EHT) calculations suggest that the easy oxidation of the (Ir(biph)} system is associated with the presence of a high-lying Ir dyz orbital. The (Ir(biph)} fragment is remarkably stable; only Br2 is able to cleave the Ir-C bonds.

AB - C-C bond cleavage of biphenylene by an Ir(I) complex via an oxidation addition generates the biph (=biphenyl-2,2'-diyl) ligand. The resulting compound is treated with PPh3 to give [Ir(PPh3)2(biph)Cl], having a 16 e five-coordinate structure lying between Y and T geometries, being closer to a Y, which is rationalized on theoretical grounds. The complex [Ir(PMe3)3-(biph)Cl] can be oxidized quasi-reversibly to an Ir(IV) species. Oxidation with NOEF4 gives the unusual Ir(IV) boryl compound [Ir(PMe3)3(biphBF)Cl]+, which has been isolated and structurally characterized. Extended Hückel (EHT) calculations suggest that the easy oxidation of the (Ir(biph)} system is associated with the presence of a high-lying Ir dyz orbital. The (Ir(biph)} fragment is remarkably stable; only Br2 is able to cleave the Ir-C bonds.

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JO - Organometallics

JF - Organometallics

IS - 3

ER -

Geometrically Distorted and Redox-Active Organometallic Iridium Complexes Containing Biphenyl-2,2'-diyl

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