Stadler Benedek, Gorgas Nikolaus, White Andrew J P, Crimmin Mark R
Department of Chemistry Imperial College London White City London W12 0BZ UK.
Institute of Applied Synthetic Chemistry Vienna University of Technology Getreidemarkt 9 1060 Vienna Austria.
Angew Chem Weinheim Bergstr Ger. 2023 Apr 11;135(16):e202219212. doi: 10.1002/ange.202219212. Epub 2023 Mar 9.
Herein we present the first double deprotonation of acetonitrile (CHCN) using two equivalents of a bimetallic iron-aluminium complex. The products of this reaction contain an exceeding simple yet rare [CHCN] dianion moiety that bridges two metal fragments. DFT calculations suggest that the bonding to the metal centres occurs through heavily polarised covalent interactions. Mechanistic studies reveal the intermediacy of a monomeric [CHCN] complex, which has been characterised in situ. Our findings provide an important example in which a bimetallic metal complex achieves a new type of reactivity not previously encountered with monometallic counterparts. The isolation of a [CHCN] dianion through simple deprotonation of CHCN also offers the possibility of establishing a broader chemistry of this motif.
在此，我们展示了使用两当量双金属铁 - 铝配合物对乙腈（CH₃CN）进行首次双去质子化反应。该反应产物包含一个极其简单却罕见的[CH₂CN]²⁻二价阴离子部分，它桥连两个金属片段。密度泛函理论计算表明，与金属中心的键合是通过高度极化的共价相互作用发生的。机理研究揭示了单体[CH₂CN]配合物的中间体，该中间体已通过原位表征。我们的研究结果提供了一个重要的例子，即双金属配合物实现了一种新型反应活性，这是单金属配合物以前未曾遇到过的。通过对CH₃CN进行简单去质子化来分离[CH₂CN]²⁻二价阴离子，也为建立该基序更广泛的化学性质提供了可能性。
