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.

过渡金属-羰基配合物是常见的有机金属试剂，具有金属-CO 键。这些配合物已被证明是适用于各种应用的强大催化剂。相比之下，硅-羰基配合物、有机硅试剂有望成为过渡金属羰基化合物的环保替代品，在很大程度上仍然难以捉摸。它们主要在理论上和/或通过低温基质隔离研究进行了探索，但它们的不稳定性通常排除了在环境条件下的隔离。在这里，我们介绍了稳定的甲硅烷基取代的硅-羰基配合物的合成、分离和完整表征，以及键合分析。最初的反应性研究显示了 CO 释放的例子，这可以通过热或光化学诱导，以及 CO 部分的取代和功能化。重要的是，配合物表现出很强的 Si-CO 键合，CO→Siσ -donation 和 Si→CO π -backbonding，这让人想起过渡金属羰基化合物。丰富的半金属硅和稀有过渡金属之间的这种相似性可能为硅基催化的发展提供新的机会。