Raubenheimer H G
Department of Chemistry and Polymer Science, University of Stellenbosch, Matieland 7602, South Africa.
Dalton Trans. 2014 Dec 7;43(45):16959-73. doi: 10.1039/c4dt01943a.
Exciting new variations in Fischer-type carbene complex composition and reactivity have been realised by following or modifying well-established synthetic approaches such as metal carbonyl functionalization and modification of existing carbene ligands. The formation of targeted complexes for organic synthesis, carbene-containing chelates, and polynuclear carbene complexes, by employing 'click chemistry', warrants discussion. Transmetallation and α,α-dehydrogenation of ethers and amines have come into their own as viable synthetic methods to access carbene complexes with unique properties and activities. Successful mediation of carbene complex formation with pincer ligands has proved its worth. Quantum chemistry has become essential for supporting or initiating mechanistic proposals, but heuristic approaches such as invoking the vinylology principle to describe substituted phenylcarbene complexes are still valuable in the interpretation of bonding properties and the classification of complex types. Electrochemical studies now also constitute a powerful part of the experimental characterization tool kit.
通过遵循或改进成熟的合成方法，如金属羰基官能化和对现有卡宾配体的修饰，费舍尔型卡宾配合物的组成和反应性实现了令人兴奋的新变化。采用“点击化学”形成用于有机合成的目标配合物、含卡宾的螯合物和多核卡宾配合物，值得讨论。醚和胺的金属转移和α,α-脱氢已成为获得具有独特性质和活性的卡宾配合物的可行合成方法。用钳形配体成功介导卡宾配合物的形成已证明了其价值。量子化学对于支持或提出机理建议已变得至关重要，但诸如援引乙烯学原理来描述取代苯基卡宾配合物等启发式方法在解释键合性质和配合物类型分类方面仍然很有价值。电化学研究现在也构成了实验表征工具包的一个强大组成部分。
