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Query: EC:3.4.16.2 (
PCP
)
3,761
document(s) hit in 31,850,051 MEDLINE articles (0.00 seconds)
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.
...
PMID:Distinct thermodynamics for the formation and cleavage of N-H bonds in aniline and ammonia. Directly-observed reductive elimination of ammonia from an isolated amido hydride complex. 1459 86
