School of Chemistry University of Nottingham, NG7 2RD, UK.
Department of Chemistry, University of York, York, YO10 5DD, UK.
Chem Soc Rev. 2022 Jul 4;51(13):5300-5329. doi: 10.1039/d1cs00826a.
The purpose of this Tutorial Review is to outline the fundamental photochemistry of metal carbonyls, and to show how the advances in technology have increased our understanding of the detailed mechanisms, particularly how relatively simple experiments can provide deep understanding of complex problems. We recall some important early experiments that demonstrate the key principles underlying current research, concentrating on the binary carbonyls and selected substituted metal carbonyls. At each stage, we illustrate with examples from recent applications. This review first considers the detection of photochemical intermediates in three environments: glasses and matrices; gas phase; solution. It is followed by an examination of the theory underpinning these observations. In the final two sections, we briefly address applications to the characterization and behaviour of complexes with very labile ligands such as N, H and alkanes, concentrating on key mechanistic points, and also describe some principles and examples of photocatalysis.
本教程综述的目的是概述金属羰基化合物的基本光化学，并展示技术的进步如何增进了我们对详细机制的理解，特别是相对简单的实验如何能够提供对复杂问题的深入理解。我们回顾了一些重要的早期实验，这些实验证明了当前研究的基础关键原则，重点关注二元羰基化合物和选定的取代金属羰基化合物。在每个阶段，我们都用来自最近应用的示例来说明。本综述首先考虑在三种环境中检测光化学反应中间体：玻璃和基质、气相和溶液。然后，我们考察了这些观察结果的理论基础。在最后两节中，我们简要介绍了应用于非常不稳定配体（如 N、H 和烷烃）的配合物的特性和行为，重点介绍关键的机理要点，还描述了光催化的一些原理和示例。
