Homolytic Cleavage of a B-B Bond by the Cooperative Catalysis of Two Lewis Bases: Computational Design and Experimental Verification

Guoqiang Wang; Honglin Zhang; Jiyang Zhao; Wei Li; Jia Cao; Chengjian Zhu; Shuhua Li

doi:10.1002/anie.201511917

Homolytic Cleavage of a B-B Bond by the Cooperative Catalysis of Two Lewis Bases: Computational Design and Experimental Verification

Angew Chem Int Ed Engl. 2016 May 10;55(20):5985-9. doi: 10.1002/anie.201511917. Epub 2016 Apr 8.

Authors

Guoqiang Wang¹, Honglin Zhang², Jiyang Zhao¹, Wei Li¹, Jia Cao¹, Chengjian Zhu³, Shuhua Li⁴

Affiliations

¹ Key Laboratory of Mesoscopic Chemistry of Ministry of Education, Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, P.R. China.
² State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, P.R. China.
³ State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, P.R. China. cjzhu@nju.edu.cn.
⁴ Key Laboratory of Mesoscopic Chemistry of Ministry of Education, Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, P.R. China. shuhua@nju.edu.cn.

PMID: 27061603
DOI: 10.1002/anie.201511917

Abstract

Density functional theory (DFT) investigations revealed that 4-cyanopyridine was capable of homolytically cleaving the B-B σ bond of diborane via the cooperative coordination to the two boron atoms of the diborane to generate pyridine boryl radicals. Our experimental verification provides supportive evidence for this new B-B activation mode. With this novel activation strategy, we have experimentally realized the catalytic reduction of azo-compounds to hydrazine derivatives, deoxygenation of sulfoxides to sulfides, and reduction of quinones with B2 (pin)2 at mild conditions.

Keywords: B−B bond activation; Lewis base; computational design; cooperative activation; homolytic cleavage.

Publication types

Research Support, Non-U.S. Gov't