Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada, T2N 1N4.
J Am Chem Soc. 2013 Aug 14;135(32):11776-9. doi: 10.1021/ja406742n. Epub 2013 Aug 1.
Nickel complexes of a PC(carbene)P pincer ligand framework are described. Dehydrobromination of the precursor (PC(sp)(3)P)NiBr in the presence of a donor (PPh3 or NC(t)Bu) leads to the title complexes, which feature a rare nickel-carbene linkage as the pincer ligand anchor point. This strongly donating, nucleophilic carbene center engages in a variety of E-H bond activations (E = H, C, N, O), some of which are reversible. This represents a new mode of bond activation by ligand cooperativity in nickel pincer complexes.
本文描述了一种 PC(carbene)P 钳形配体框架的镍配合物。在供体(PPh3 或 NC(t)Bu)存在下,前体(PC(sp)(3)P)NiBr 的脱溴反应得到了标题配合物,其特征是镍-卡宾键作为钳形配体的连接点,这是一种罕见的结构。这种强给电子、亲核卡宾中心参与了各种 E-H 键的活化(E = H、C、N、O),其中一些是可逆的。这代表了镍钳形配合物中通过配体协同作用实现键活化的新模式。