Crystal structures of two PCN pincer iridium complexes and one PCP pincer carbodi­phospho­rane iridium inter­mediate: substitution of one phosphine moiety of a carbodi­phospho­rane by an organic azide

The structure of [Ir{(4-Cl-C(6)H(4)N(3))C(dppm)-κ(3) P,C,N}(dppm-κ(2) P,P′)]Cl·1.5CH(2)Cl(2)·0.5C(7)H(8) (C(57)H(48)Cl(2)IrN(3)P(4)·1.5CH(2)Cl(2)·0.5C(7)H(8)) (2), dppm = bis­(di­phenyl­phosphino)methane {systematic name: [7-(4-chloro­phen­yl)-1,1,3,3-tetra­phenyl-5,6,7-tri­aza-κN (7)-1,3λ(4)-diphospha-κP (1)-hepta-4,6-dien-4-yl][methyl­ene­bis(di­phenyl­phosphine)-κ(2) P,P′]iridium(I) chloride–di­chloro­methane–toluene (2/3/1)}, resulting from the reaction of [IrClH{C(dppm)(2)-κ(3) P,C,P)(MeCN)]Cl (1a) with 1-azido-4-chloro­benzene, shows a monocationic five-coordinate Ir(I) complex with a distorted trigonal–bipyramidal geometry. In 2, the iridium centre is coordinated by the neutral triazeneyl­idene­phospho­rane (4-Cl-C(6)H(4)N(3))C(dppm) acting as a PCN pincer ligand, and a chelating dppm unit. The structure of the coordination compound [IrCl(CN)H(C(dppm)(2)-κ(3) P,C,P)]·CH(3)CN, (C(52)H(45)ClIrNP(4)·CH(3)CN) (1b) [systematic name: chlorido­cyanidohydrido(1,1,3,3,5,5,7,7-octa­phenyl-1,3λ(5),5λ(4),7-tetra­phospha-κ(2) P (1),P (7)-hept-3-en-4-yl)iridium(III) aceto­nitrile monosolvate], prepared from 1a and KCN, reveals an octa­hedral Ir(III) central atom with a meridional PCP pincer carbodi­phospho­rane (CDP) ligand; the chloride ligand is located trans to the central carbon of the CDP functionality while the hydrido and cyanido ligands are situated trans to each other. The chiral coordination compound [Ir(CN)((4-Cl-C(6)H(4)N(3))CH(CH(P(Ph)(2))(2))-κ(3) P,C,N)(dppm-κ(2) P,P′)]·2CH(3)OH, (C(58)H(48)ClIrN(4)P(4)·2CH(3)OH) (3) (systematic name: {4-[3-(4-chloro­phen­yl)triazenido-κN (3)]-1,1,3,3-tetra­phenyl-1,3λ(5)-diphospha-κP (1)-but-2-en-4-yl}cyanido[methyl­enebis(di­phenyl­phosphine)-κ(2) P,P′]iridium(III) methanol disolvate), formed via prolonged reaction of 1-azido-4-chloro­benzene with 1b, features a six-coordinate Ir(III) central atom. The iridium centre is coordinated by the dianionic facial PCN pincer ligand [(4-Cl-C(6)H(4)N(3))CH(CH(P(Ph(2))(2))(2))], a cyanido ligand trans to the central carbon of the PCN pincer ligand and a chelating dppm unit. Complex 2 exhibits a 2:1 positional disorder of the Cl(−) anion. The CH(2)Cl(2) and C(7)H(8) solvent mol­ecules show occupational disorder, with the toluene mol­ecule exhibiting additional 1:1 positional disorder with some nearly overlying carbon atoms.