Stoichiometric and Catalytic Reactivity of Dinuclear Nickel Complexes Containing a Redox-Active Ligand

Talia J Steiman, Purdue University

Abstract

Inspired by enzymes, which often use multinuclear active sites for biological redox transformations, there has been recent interest in designing synthetic catalysts that incorporate more than one metal center. Although complexes containing metal–metal bonds have been invoked as transient intermediates in organic transformations, their general utility in catalysis has yet to be established. To address this limitation, we recently described the synthesis of well-defined dinickel complexes using a binucleating naphthyridine–diimine (NDI) pincer ligand. The redox-active π- system of the ligand reversibly stores electron equivalents, allowing Ni–Ni bonds to be stabilized across a range of unusual formal oxidation states. With this system, we have studied dinuclear variants of oxidative addition and silane activation reactions. We have also demonstrated the applications of Ni2 catalysts in reductive vinylidene insertions into C(sp2)–H bonds.

Degree

Ph.D.

Advisors

Uyeda, Purdue University.

Subject Area

Organic chemistry

COinS