Issue 12, 2015

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 hydride source, and importantly, a pathway which proceeds through a single electron reduction and H-atom transfer reaction, mediated by anthraquinone was uncovered. The latter transformation was also carried out electrochemically, at relatively positive potentials by comparison to all prior reports, thus establishing an important proof of concept for any future electrochemical B[double bond, length as m-dash]N bond reduction.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
29 יונ 2015
Accepted
24 ספט 2015
First published
01 אוק 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2015,6, 7258-7266

Author version available

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

T. J. Carter, Z. M. Heiden and N. K. Szymczak, Chem. Sci., 2015, 6, 7258 DOI: 10.1039/C5SC02348C

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