An operationally convenient, room temperature synthesis of N,N-diborylated amines via hydroboration of nitriles using a commercially available catalyst.

This report describes the synthesis, characterization, and ligand exchange studies of iridium-based, pincer complexes. ( t B u POCOP)Ir(PP h 3 ) ( t B u POCOP = 2,6-bis(di-tertbutylphosphonito)benzene) serves as a convenient source of the latent Ir(I), 14-electron species [( tBu POCOP)Ir] and is susceptible to ligand exchange chemistry; reactions with acetonitrile and pyridine afford the corresponding ( tBu POCOP)Ir(NCMe) (2) and ( tBu POCOP)Ir(Py) (3) complexes, respectively. Varying concentrations of both pyridine and acetonitrile, the kinetic and thermodynamic parameters of the ligand exchange process between ( tBu POCOP)Ir(PPh 3 ) and L (L = MeCN or pyridine) were determined by employing NMR, UV−vis spectroscopy, and density functional theory (DFT) calculations to measure the relevant equilibria. A discussion of these results allows us to address whether phosphine displacement occurs via an associative or a dissociative pathway.

A recoverable catalyst system has been developed and its application in both Suzuki-Miyaura and Negishi coupling reactions has been demonstrated. We have also investigated the nature of the active catalyst...