Sherbow Tobias J, Li Keyan, Zakharov Lev N, Pluth Michael D
Department 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.
Dalton Trans. 2022 Oct 4;51(38):14563-14567. doi: 10.1039/d2dt02809c.
The [B(BuIm)] 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 B(BuIm)ZnCl (1) complex can be formed deprotonation of [B(BuIm)][OTf] followed by the addition of ZnCl. Salt metathesis reaction with nucleophilic -BuLi yields the highly carbon-rich zinc coordination complex B(BuIm)ZnBu (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][S], leads to the formation of a tetrahedral zinc tetrasulfido complex protonation of one carbene donor to form B(BuIm)(BuImH)Zn(κ-S) (3).
自2006年首次报道以来，[B(BuIm)]配体因其能够稳定高活性的第一排过渡金属配合物而受到越来越多的关注。在这项工作中，我们研究了该配体与氧化还原惰性锌的配位化学，以了解锌金属中心在如此强的配位环境中的行为。[B(BuIm)][OTf]去质子化后加入ZnCl可形成B(BuIm)ZnCl (1)配合物。与亲核的-BuLi进行盐复分解反应可得到具有三个卡宾原子供体和一个碳负离子供体的高度富碳锌配位配合物B(BuIm)ZnBu (2)。相比之下，配合物1与亲核性较弱的多硫化物试剂[K·18-C-6][S]反应，会导致形成一个四面体锌四硫代配合物，一个卡宾供体质子化形成B(BuIm)(BuImH)Zn(κ-S) (3)。
