Two-State Reactivity Mechanism of Benzene C-C Activation by Trinuclear Titanium Hydride

J Am Chem Soc. 2016 Sep 7;138(35):11069-72. doi: 10.1021/jacs.6b02433. Epub 2016 Aug 24.

Abstract

The cleavage of inert C-C bonds is a central challenge in modern chemistry. Multinuclear transition metal complexes would be a desirable alternative because of the synergetic effect of multiple metal centers. In this work, carbon-carbon bond cleavage and rearrangement of benzene by a trinuclear titanium hydride were investigated using density functional theory. The reaction occurs via a novel "two-state reactivity" mechanism. The important elementary steps consist of hydride transfer, benzene coordination, dehydrogenation, oxidative addition, hydride-proton exchange, and reductive elimination. Most importantly, the ground-state potential energy surface switches from nearly degenerate triplet and antiferromagnetic singlet states to a closed-shell singlet state in the dearomatization of benzene, which effectively decreases the activation barrier. Furthermore, the roles of the transition metal centers and hydrides were clarified.

Publication types

  • Research Support, Non-U.S. Gov't