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Crystal structures of the [Ir^III{C(C₄H₆O₂)(dppm)-κ³ P,C,O}(dppm)H](CF₃O₃S)₂ and [Ir^III{C(C₄H₆O₂)(dppm)-κ² P,C}(CO)(dppm)H](CF₃O₃S)₂ phosphorus ylide complexes, generated by a Wittig-type carbon-carbon coupling reaction of a carbodiphospho-rane PCP ligand system.

ABSTRACT: The reaction of [Ir^III{C(dppm)₂-κ³ P,C,P'}ClH(NH₃C₂)]Cl with ethyl diazo-acetate, a well known C=C coupling reagent, leads to the formation of a C=C unit, accompanied by N₂ abstraction, reorganization of a dppm subunit and, considered as a whole, to the transformation of the PCP pincer carbodi-phospho-rane system to a phospho-rus ylide ligand. After removal of the halogenides, the iridium center is stabilized by the carbonyl O atom through the formation of a five-membered chelate ring. A PCO pincer ligand system is thereby generated, which coordinates the iridium(III) atom threefold in a facial manner. The phospho-rus electron-donor atoms and the ylide carbon atom of the resulting [Ir^III{C(C₄H₆O₂)(dppm)-κ³ P,C,O}(dppm)H](CF₃O₃S)₂ complex, also termed as [bis-(di-phenyl-phosphan-yl)methane]({[(di-phenyl-phosphan-yl)meth-yl]di-phenyl-phosphanyl-idene}(eth-oxy-oxoethanyl-idene)methanyl-idene-κ³ P,C,O)hydridoiridium(III) bis-(tri-fluoro-methane-sulfonate), are in plane and the hydrido ligand and the carbonyl O atom are located trans to each other, perpendicular to the meridional plane. The addition of carbon monoxide causes a replacement of the carbonyl O atom of the acetate subunit by a carbonyl ligand, thereby creating [bis-(di-phenyl-phosphan-yl)methane]-carbon-yl({[(di-phenyl-phosphan-yl)meth-yl]di-phenyl-phosphanyl-idene}(eth-oxy-oxoethanyl-idene)methanyl-idene-κ² P,C}hydridoiridium(III) bis-(tri-fluoro-methane-sulfonate)-di-chloro-methane-ethyl acetate (6/2/3) or, more simply, [Ir^III{C(C₄H₆O₂)(dppm)-κ² P,C}(CO)(dppm)H](CF₃O₃S)₂·0.33CH₂Cl₂·0.5C₄H₈O₂. One tri-fluoro-meth-ane-sulfonate counter-ion of 3 shows positional disorder in a 2:1 ratio. Complex 4 shows pseudo-merohedral twinning (matrix: 0 0 0 0 1 0 1). The di-chloro-methane solvent is disordered over two orientations with occupation factors of 0.5 and 0.166.

SUBMITTER: Schlapp-Hackl I

PROVIDER: S-EPMC6218904 | biostudies-literature | 2018 Nov

REPOSITORIES: biostudies-literature

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Crystal structures of the [IrIII{C(C4H6O2)(dppm)-κ3 P,C,O}(dppm)H](CF3O3S)2 and [IrIII{C(C4H6O2)(dppm)-κ2 P,C}(CO)(dppm)H](CF3O3S)2 phosphorus ylide complexes, generated by a Wittig-type carbon-carbon coupling reaction of a carbodiphospho-rane PCP ligand system.

Schlapp-Hackl Inge I Pauer Bettina B Falschlunger Christoph C Schuh Walter W Kopacka Holger H Wurst Klaus K Peringer Paul P

Acta crystallographica. Section E, Crystallographic communications 20181023 Pt 11

The reaction of [IrIII{C(dppm)2-κ3 P,C,P'}ClH(NH3C2)]Cl with ethyl diazo-acetate, a well known C=C coupling reagent, leads to the formation of a C=C unit, accompanied by N2 abstraction, reorganization of a dppm subunit and, considered as a whole, to the transformation of the PCP pincer carbodi-phospho-rane system to a phospho-rus ylide ligand. After removal of the halogenides, the iridium center is stabilized ...[more]

PMID: 30443398

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Project description: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-κ2 P 1,P 9)-(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)-κ 2P,C)(dppm-κ 2P,P')]I(I3)·0.5I2·CH3OH·0.5CH2Cl2 {4, systematic name: (4-diazo-1,1,3,3,-tetra-phenyl-1,3λ4-diphosphabutan-4-yl-κP 1)iodido[methyl-enebis(di-phenyl-phosphine)-κ2 P,P'](phenyl-methanimine-κN)iridium(III) iodide-triiodide-di-chloro-methane-iodine-methanol (2/2/1/1/2)}, accessed via treatment of the triazeneyl-idene-phospho-rane complex [Ir((BnN3)C(dppm)-κ 3P,C,N)(dppm-κ 2P,P')]Cl with hydro-iodic acid, consists of a dicationic six-coordinate IrIII complex, coordinated by a bidentate diazo-methyl-ene-phospho-rane, a benzaldimine, a chelating dppm moiety and an iodido ligand. The phospho-rus atoms of the chelating dppm are trans to the central carbon atom of the diazo-methyl-ene-phospho-rane and the iodide ligand, respectively. Both an iodide and a triiodide moiety function as counter-ions. The aceto-nitrile solvent mol-ecules in 3 are severely disordered in position and occupation. In 4, the I3 - anion is positionally disordered (ratio roughly 1:1), as is the I- anion with a ratio of 9:1. The di-chloro-methane solvent mol-ecule lies near a twofold rotation axis (disorder) and was refined with an occupancy of 0.5. Another disorder occurs for the solvent methanol with a 1:1 ratio.

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Crystal structures of the [Ir^III{C(C₄H₆O₂)(dppm)-κ³ P,C,O}(dppm)H](CF₃O₃S)₂ and [Ir^III{C(C₄H₆O₂)(dppm)-κ² P,C}(CO)(dppm)H](CF₃O₃S)₂ phosphorus ylide complexes, generated by a Wittig-type carbon-carbon coupling reaction of a carbodiphospho-rane PCP ligand system.

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