Crystal structures of [IrCl2 (NHCHPh)((dppm)(C(N2 dppm))-κ3P ,C ,P ')]Cl·5.5MeCN and [IrI(NHCHPh)(((dppm)C(N2 ))-κ2P ,C )(dppm-κ2P ,P ')]I(I3 )·0.5I2 ·MeOH·0.5CH2 Cl2 : triazene fragmentation in a PCN pincer iridium complex

Acta Crystallographica. Section E, Crystallographic Communications
Bettina PauerPaul Peringer

Abstract

The structure of [IrCl2(C58H51N3P4)]Cl·5.5CH3CN or [IrCl2(NHCHPh)(((dppm)C(N2dppm))-κ 3P,C,P)]Cl·5.5CH3CN [3, dppm = bis-(di-phenyl-phos-phino)methane; systematic name: di-chlorido(1,1,3,3,7,7,9,9-octa-phenyl-4,5-di-aza-1,3λ5,7λ4,9-tetra-phosphanona-3,5-dien-6-yl-κ2P1,P9)-(phenyl-methanimine-κN)iridium(III) chloride aceto-nitrile hemihendeca-solvate], resulting from an oxygen-mediated cleavage of a triazeneyl-idene-phospho-rane ligand producing a diazo-methyl-ene-phospho-rane and a nitrene moiety, which in turn rearrange via a Staudinger reaction and a 1,2-hydride shift to the first title complex, involves a six-coordinate IrIII complex cation coordinated by a facial PCP pincer ligand, a benzaldimine and two chlorido ligands. The pincer system features a five- and a seven-membered ring, with the central divalent carbon of the PCP pincer ligand being connected to a phosphine and a diazo-phospho-rane. The chlorido ligands are positioned trans to the central carbon atom and to the phospho-rus donor of the seven-membered ring of the pincer system, respectively. A chloride ion serves as counter-ion for the monocationic complex. The structure of [IrI(C26H22N2P2)(C26H22P2)(C6H7N)]I(I3)·0.5I2·CH3OH·0.5CH2Cl2 or [IrI(NHCHPh)((dppm)C(N2)...Continue Reading

References

Mar 23, 2005·Angewandte Chemie·Tetsuro MurahashiChristopher C Cummins
Dec 15, 2007·Inorganic Chemistry·Gabriele AlbertinSoledad García-Fontan
Dec 25, 2007·Acta Crystallographica. Section A, Foundations of Crystallography·George M Sheldrick
Nov 28, 2008·Angewandte Chemie·Eddie L Myers, Ronald T Raines
Nov 8, 2011·Acta Crystallographica. Section E, Structure Reports Online·Xiao PengXue Chen
Feb 11, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Christian ReitsamerPaul Peringer
Jan 9, 2015·Acta Crystallographica. Section C, Structural Chemistry·George M Sheldrick
Nov 26, 2015·Chemistry : a European Journal·Valerij A NikolaevMurat B Supurgibekov
Apr 7, 2016·Acta Crystallographica Section B, Structural Science, Crystal Engineering and Materials·Colin R GroomSuzanna C Ward
Jun 29, 2018·Acta Crystallographica. Section E, Crystallographic Communications·Gabriel Julian PartlPaul Peringer

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Citations

May 2, 2020·Chemical Reviews·Christin BednarekStefan Bräse

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Methods Mentioned

BETA
NMR

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