Discovery of low energy pathways to metal-mediated B[double bond, length as m-dash]N bond reduction guided by computation and experiment.

ABSTRACT: This manuscript describes a combination of DFT calculations and experiments to assess the reduction of borazines (B-N heterocycles) by η⁶-coordination to Cr(CO)₃ or [Mn(CO)₃]⁺ fragments. The energy requirements for borazine reduction are established as well as the extent to which coordination of borazine to a transition metal influences hydride affinity, basicity, and subsequent reduction steps at the coordinated borazine molecule. Borazine binding to M(CO)₃ fragments decreases the thermodynamic hydricity by >30 kcal mol^-1, allowing it to easily accept a hydride. These hydricity criteria were used to guide the selection of appropriate reagents for borazine dearomatization. Reduction was achieved with an H₂-derived

SUBMITTER: Carter TJ 

PROVIDER: S-EPMC5512141 | biostudies-literature | 2015 Dec

REPOSITORIES: biostudies-literature