Crystal structures of [IrCl(2)(NHCHPh)((dppm)(C(N(2)dppm))-κ(3) P,C,P′)]Cl·5.5MeCN and [IrI(NHCHPh)(((dppm)C(N(2)))-κ(2) P,C)(dppm-κ(2) P,P′)]I(I(3))·0.5I(2)·MeOH·0.5CH(2)Cl(2): triazene fragmentation in a PCN pincer iridium complex

The structure of [IrCl(2)(C(58)H(51)N(3)P(4))]Cl·5.5CH(3)CN or [IrCl(2)(NHCHPh)(((dppm)C(N(2)dppm))-κ(3)P,C,P)]Cl·5.5CH(3)CN [3, dppm = bis­(di­phenyl­phos­phino)methane; systematic name: di­chlorido(1,1,3,3,7,7,9,9-octa­phenyl-4,5-di­aza-1,3λ(5),7λ(4),9-tetra­phosphanona-3,5-dien-6-yl-κ(2) P (1),P (9))­(phenyl­methanimine-κN)iridium(III) chloride aceto­nitrile hemihendeca­solvate], resulting from an oxygen-mediated cleavage of a triazeneyl­idene­phospho­rane ligand producing a diazo­methyl­ene­phospho­rane 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 Ir(III) 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 diazo­phospho­rane. The chlorido ligands are positioned trans to the central carbon atom and to the phospho­rus 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(C(26)H(22)N(2)P(2))(C(26)H(22)P(2))(C(6)H(7)N)]I(I(3))·0.5I(2)·CH(3)OH·0.5CH(2)Cl(2) or [IrI(NHCHPh)((dppm)C(N(2))-κ(2)P,C)(dppm-κ(2)P,P′)]I(I(3))·0.5I(2)·CH(3)OH·0.5CH(2)Cl(2) {4, systematic name: (4-diazo-1,1,3,3,-tetra­phenyl-1,3λ(4)-diphosphabutan-4-yl-κP (1))iodido[methyl­enebis(di­phenyl­phosphine)-κ(2) P,P′](phenyl­methanimine-κN)iridium(III) iodide–triiodide–di­chloro­methane–iodine–methanol (2/2/1/1/2)}, accessed via treatment of the triazeneyl­idene­phospho­rane complex [Ir((BnN(3))C(dppm)-κ(3)P,C,N)(dppm-κ(2)P,P′)]Cl with hydro­iodic acid, consists of a dicationic six-coordinate Ir(III) complex, coordinated by a bidentate diazo­methyl­ene­phospho­rane, a benzaldimine, a chelating dppm moiety and an iodido ligand. The phospho­rus atoms of the chelating dppm are trans to the central carbon atom of the diazo­methyl­ene­phospho­rane and the iodide ligand, respectively. Both an iodide and a triiodide moiety function as counter-ions. The aceto­nitrile solvent mol­ecules in 3 are severely disordered in position and occupation. In 4, the I(3) (−) anion is positionally disordered (ratio roughly 1:1), as is the I(−) anion with a ratio of 9:1. The di­chloro­methane solvent mol­ecule 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.