The insertion of an iridium complex into an N-H bond in ammonia leads to a stable monomeric amido hydride complex in solution at room temperature. This reaction advances the transition-metal coordination chemistry of ammonia beyond its role for more than a century as an ancillary ligand. The precursor for this insertion reaction is an iridium(I) olefin complex with an aliphatic ligand containing one carbon and two phosphorus donor atoms. Kinetic and isotopic labeling studies indicate that olefin dissociates to give a 14-electron iridium(I) fragment, which then reacts with ammonia. This cleavage of the N-H bond under neutral conditions provides a foundation on which to develop future mild catalytic transformations of ammonia, such as olefin hydroamination and arene oxidative amination.
The reactions of aryl and alkylamines with the (PCP)Ir fragment (PCP = 1,3-di-tert-butylphosphinobenzene) were studied to determine the reactivities and stabilities of amine and amido hydride complexes relative to C-H activation products. Reaction of aniline with the (PCP)Ir unit generated from (PCP)IrH2 and norbornene resulted in the N-H oxidative addition product (PhNH)(H)Ir(PCP) (1a). In contrast, reaction of this fragment with ammonia gave the ammonia complex (NH3)Ir(PCP) (2). The amido hydride complex that would be formed by oxidative addition of ammonia, (PCP)Ir(NH2)(H) (1b), was generated independently by deprotonation of the ammonia complex (NH3)Ir(H)(Cl)(PCP) (3) with KN(SiMe3)2 at low temperature. This amido hydride complex underwent reductive elimination at room temperature to form the ammonia complex 2. Addition of CO to anilide complex 1a gave (PCP)Ir(PhNH)(H)(CO) (4a). Addition of CNtBu to terminal amido complex 1b formed (PCP)Ir(NH2)(H)(CNtBu) (4b), the first structurally characterized iridium amido hydride. Complexes 4a and 4b underwent reductive elimination of aniline and ammonia; parent amido complex 4b reacted faster than anilide 4a. These observations suggest distinct thermodynamics for the formation and cleavage of N-H bonds in aniline and ammonia. Complexes 1a, 2, 4a, and 4b were characterized by single-crystal X-ray diffraction methods.
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