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The Mechanism of Acceptorless Amine Double Dehydrogenation by N,N,N-Amide Ruthenium(II) Hydrides: A Combined Experimental and Computational Study

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journal contribution
posted on 2016-06-24, 15:21 authored by Lillian V. A. Hale, Tanmay Malakar, Kuei-Nin T. Tseng, Paul M. Zimmerman, Ankan Paul, Nathaniel K. Szymczak
A detailed mechanistic analysis of the acceptorless double dehydrogenation of primary amines to form nitriles by HRu­(bMepi)­(PPh3)2 (1, bMepi = 1,3-bis­(6′-methyl-2′-pyridylimino)­isoindolate) is presented. The presence of the ortho-CH3 substituents on bMepi is critical for amine dehydrogenation, and no catalysis was observed with HRu­(bpi)­(PPh3)2 (1-bpi, bpi = 1,3-bis­(2′-pyridylimino)­isoindolate). Outer-sphere, inner-sphere, and hemilabile pathways were evaluated through ligand substitution and kinetic studies, catalyst modifications, and computational analysis. We propose an inner-sphere mechanism in which a Ru–hydride is protonated by coordinated amine followed by H2 release, which forms a Ru–amido intermediate. The stability of Ru–amido species was evaluated through NBO, AIM, and NCI analyses, revealing steric pressure as well as weak noncovalent interactions between the coordinated amido nitrogen atom and the ortho-alkyl substituents, and these interactions impact the overall thermodynamic profile for amine dehydrogenation by 1. Finally, the preference for double dehydrogenation over the transamination reaction is attributed to a high binding constant of the imine intermediate and fast kinetics of a second dehydrogenation.

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