德国慕尼黑工业大学的Shigeyoshi Inoue小组取得一项新突破。他们开发出甲烷硅基化的硅-羰基化合物能够模拟过渡金属羰基配合物，用于催化反应。 2020年10月19日出版的《自然化学》发表了这项成果。

在这里，课题组研究人员介绍了稳定的甲硅烷基取代的硅-羰基化合物的合成、分离和全面表征，并进行了成键作用分析。最初的反应性研究表明有CO释放的例子，这些反应可以由热效应或者光化学效应引发，同时还观察到CO基团的取代和功能化。重要的是，配合物表现出很强的Si-CO成键作用，包括CO→Si σ配位键和Si→CO的π反键，这和过渡金属羰基化合物相似。这种丰富的半金属硅和稀有过渡金属间的相似性为基于硅的催化的发展提供了新的机遇。

据悉，过渡金属羰基化合物是含有金属-羰基键的常用有机金属试剂。这些复合物被证明是对多种应用有效的强大的催化剂。相比之下，有机硅试剂被认为是过渡金属羰基化合物的更为环保的替代品，但对硅-羰基化合物了解仍然有限。对硅-羰基化合物的研究多数停留在理论和/或通过低温下基质分离研究，它们的不稳定性使得在环境条件下进行分离通常无法实现。

附：英文原文

Title: Silylated silicon–carbonyl complexes as mimics of ubiquitous transition-metal carbonyls

Author: Dominik Reiter, Richard Holzner, Amelie Porzelt, Philipp Frisch, Shigeyoshi Inoue

Issue&Volume: 2020-10-19

Abstract: Transition-metal–carbonyl complexes are common organometallic reagents that feature metal–CO bonds. These complexes have proven to be powerful catalysts for various applications. By contrast, silicon–carbonyl complexes, organosilicon reagents poised to be eco-friendly alternatives for transition-metal carbonyls, have remained largely elusive. They have mostly been explored theoretically and/or through low-temperature matrix isolation studies, but their instability had typically precluded isolation under ambient conditions. Here we present the synthesis, isolation and full characterization of stable silyl-substituted silicon–carbonyl complexes, along with bonding analysis. Initial reactivity investigations showed examples of CO liberation, which could be induced either thermally or photochemically, as well as substitution and functionalization of the CO moiety. Importantly, the complexes exhibit strong Si–CO bonding, with CO→Si σ-donation and Si→CO π-backbonding, which is reminiscent of transition-metal carbonyls. This similarity between the abundant semi-metal silicon and rare transition metals may provide new opportunities for the development of silicon-based catalysis.

DOI: 10.1038/s41557-020-00555-4

Source: https://www.nature.com/articles/s41557-020-00555-4