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Updated: Aug 29, 2025

Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides
Published on: May 26, 2019
Synthesis and reactivity of a tris(carbene) zinc chloride complex
Tobias J Sherbow1, Keyan Li1, Lev N Zakharov1
1Department of Chemistry and Biochemistry, Materials Science Institute, Knight Campus for Accelerating Scientific Impact, and Institute of Molecular Biology, University of Oregon, Eugene, Oregon, 97403-1253, USA. pluth@uoregon.edu.
Abstract:
The [PhB(BuIm)3]1- ligand has gained increased attention since it was first reported in 2006 due to its ability to stabilize highly reactive first row transition metal complexes. In this work, we investigate the coordination chemistry of this ligand with redox-inert zinc to understand how a zinc metal center behaves in such a strong coordinating environment. The PhB(BuIm)3ZnCl (1) complex can be formed via deprotonation of [PhB(BuIm)3][OTf]2 followed by the addition of ZnCl2. Salt metathesis reaction with nucleophilic n-BuLi yields the highly carbon-rich zinc coordination complex PhB(BuIm)3ZnBu (2) with three carbene atom donors and one carbanion donor. In contrast, reaction of complex 1 with a less nucleophilic polysulfide reagent, [K.18-C-6]2[S4], leads to the formation of a tetrahedral zinc tetrasulfido complex via protonation of one carbene donor to form PhB(BuIm)2(BuImH)Zn(κ2-S4) (3).
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