Synthesis and Reactivity of the Monomeric Late‐Transition‐Metal Parent Amido Complex [Ir(Cp*)(PMe 3 )(Ph)(NH 2 )]

The late‐transition‐metal parent amido compound [Ir(Cp*)(PMe 3 )(Ph)(NH 2 )] ( 2 ) has been synthesized by deprotonation of the corresponding ammine complex [Ir(Cp*)(PMe 3 )(Ph)(NH 3 )][OTf] ( 6 ) with KN(SiMe 3 ) 2 . An X‐ray structure determination has ascertained its monomeric nature. Proton‐transfer studies indicate that 2 can successfully deprotonate p ‐nitrophenylacetonitrile, aniline, and phenol. Crystallographic analysis has revealed that the ion pair [Ir(Cp*)(PMe 3 )(Ph)(NH 3 )][OPh] ( 8 ) exists as a hydrogen‐bonded dimer in the solid state. Reactions of 2 with isocyanates and carbodiimides lead to overall insertion of the heterocumulenes into the NH bond of the Ir‐bonded amido group, demonstrating the ability of 2 to act as an efficient nucleophile. Intriguing reactivity is observed when amide 2 reacts with CO or 2,6‐dimethylphenyl isocyanide. η 4 ‐Tetramethylfulvene complexes [Ir(η 4 ‐C 5 Me 4 CH 2 )(PMe 3 )(Ph)(L)] (L=CO ( 15 ), CNC 6 H 3 ‐2,6‐(CH 3 ) 2 ( 16 )) are formed in solution through displacement of the amido group by the incoming ligand followed by deprotonation of a methyl group on the Cp* ring and liberation of ammonia. Conclusive evidence for the presence of the Ir‐bonded η 4 ‐tetramethylfulvene moiety in the solid state has been provided by an X‐ray diffraction study of complex 16 .