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The reaction of [{Ir(µ-Cl)(coe) 2 } 2 ] ( 1 , coe =  cis -cyclooctene) with the bulky tertiary phosphane P( o -tolyl) 3  in dichloromethane at room temperature was investigated. It afforded in good yield the tri-coordinate iridium(I) complex [IrCl{P( o -tolyl) 3 } 2 ] ( 2 ) which was characterized in the solid state by a single-crystal X-ray diffraction study revealing a molecular structure of a rare tri-coordinate complex. The iridium(I) complex is stabilized by an agostic interaction of a hydrogen atom from the methyl group of the bulky phosphane ligand to fill the fourth unsaturated coordination site. The title compound crystallized from dichloromethane/diethyl ether as orange crystals in a mixture of two modifications (monoclinic  P 2 1 / c ,  2a , and orthorhombic  Pbca ,  2b ). The co-existence of the two components as a nearly 1:1 mixture in the crystalline bulk material was supported by solid-state  31 P{ 1 H} NMR measurements.

Ein neuartiger T-förmiger 14-Elektronen-Iridium(I)-Komplex stabilisiert durch eine agostische Ir–H-Wechselwirkung