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Issue 12, 2015
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Discovery of low energy pathways to metal-mediated B[double bond, length as m-dash]N bond reduction guided by computation and experiment

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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

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Article information


Submitted
29 Jun 2015
Accepted
24 Sep 2015
First published
01 Oct 2015

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2015,6, 7258-7266
Article type
Edge Article
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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