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

Research output: Contribution to journalArticle

61 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 PPh 3 to give [Ir(PPh 3 ) 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(PMe 3 ) 3 -(biph)Cl] can be oxidized quasi-reversibly to an Ir(IV) species. Oxidation with NOEF 4 gives the unusual Ir(IV) boryl compound [Ir(PMe 3 ) 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 Br 2 is able to cleave the Ir-C bonds.

Original languageEnglish
Pages (from-to)1168-1175
Number of pages8
JournalOrganometallics
Volume14
Issue number3
DOIs
Publication statusPublished - 1995 Jan 1

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Iridium
Organometallics
iridium
Oxidation
oxidation
cleavage
fragments
Ligands
orbitals
ligands
Geometry
geometry
Oxidation-Reduction
diphenyl

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Lu, Zheng ; Jun, Chul-Ho ; de Gala, Susan R. ; Crabtree, Robert H. ; Sigalas, Michael P. ; Eisenstein, Odile. / Geometrically Distorted and Redox-Active Organometallic Iridium Complexes Containing Biphenyl-2,2'-diyl. In: Organometallics. 1995 ; Vol. 14, No. 3. pp. 1168-1175.
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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 PPh 3 to give [Ir(PPh 3 ) 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(PMe 3 ) 3 -(biph)Cl] can be oxidized quasi-reversibly to an Ir(IV) species. Oxidation with NOEF 4 gives the unusual Ir(IV) boryl compound [Ir(PMe 3 ) 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 d yz orbital. The (Ir(biph)} fragment is remarkably stable; only Br 2 is able to cleave the Ir-C bonds.",
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Geometrically Distorted and Redox-Active Organometallic Iridium Complexes Containing Biphenyl-2,2'-diyl. / Lu, Zheng; Jun, Chul-Ho; de Gala, Susan R.; Crabtree, Robert H.; Sigalas, Michael P.; Eisenstein, Odile.

In: Organometallics, Vol. 14, No. 3, 01.01.1995, p. 1168-1175.

Research output: Contribution to journalArticle

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AU - Lu, Zheng

AU - Jun, Chul-Ho

AU - de Gala, Susan R.

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AU - Eisenstein, Odile

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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 PPh 3 to give [Ir(PPh 3 ) 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(PMe 3 ) 3 -(biph)Cl] can be oxidized quasi-reversibly to an Ir(IV) species. Oxidation with NOEF 4 gives the unusual Ir(IV) boryl compound [Ir(PMe 3 ) 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 Br 2 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 PPh 3 to give [Ir(PPh 3 ) 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(PMe 3 ) 3 -(biph)Cl] can be oxidized quasi-reversibly to an Ir(IV) species. Oxidation with NOEF 4 gives the unusual Ir(IV) boryl compound [Ir(PMe 3 ) 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 Br 2 is able to cleave the Ir-C bonds.

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