Crystal structures of the [Ir(III){C(C(4)H(6)O(2))(dppm)-κ(3) P,C,O}(dppm)H](CF(3)O(3)S)(2) and [Ir(III){C(C(4)H(6)O(2))(dppm)-κ(2) P,C}(CO)(dppm)H](CF(3)O(3)S)(2) phosphorus ylide complexes, generated by a Wittig-type carbon-carbon coupling reaction of a carbodiphospho-rane PCP ligand system.

The reaction of [Ir(III){C(dppm)(2)-κ(3) P,C,P'}ClH(NH(3)C(2))]Cl with ethyl diazo-acetate, a well known C=C coupling reagent, leads to the formation of a C=C unit, accompanied by N(2) 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(C(4)H(6)O(2))(dppm)-κ(3) P,C,O}(dppm)H](CF(3)O(3)S)(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-κ(3) 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-κ(2) P,C}hydridoiridium(III) bis-(tri-fluoro-methane-sulfonate)-di-chloro-methane-ethyl acetate (6/2/3) or, more simply, [Ir(III){C(C(4)H(6)O(2))(dppm)-κ(2) P,C}(CO)(dppm)H](CF(3)O(3)S)(2)·0.33CH(2)Cl(2)·0.5C(4)H(8)O(2). 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.