With a growing interest in utilizing visible light to drive biocatalytic processes, several light-harvesting units and approaches have been employed to harness the synthetic potential of heme monooxygenases and carry out selective oxyfunctionalization of a wide range of substrates. While the fields of cytochrome P450 and Ru(II) photochemistry have separately been prolific, it is not until the turn of the 21st century that they converged. Non-covalent and subsequently covalently attached Ru(II) complexes were used to promote rapid intramolecular electron transfer in bacterial P450 enzymes. Photocatalytic activity with Ru(II)-modified P450 enzymes was achieved under reductive conditions with a judicious choice of a sacrificial electron donor. The initial concept of Ru(II)-modified P450 enzymes was further improved using protein engineering, photosensitizer functionalization and was successfully applied to other P450 enzymes. In this review, we wish to present the recent contributions from our group and others in utilizing Ru(II) complexes coupled with P450 enzymes in the broad context of photobiocatalysis, protein assemblies and chemoenzymatic reactions. The merging of chemical catalysts with the synthetic potential of P450 enzymes has led to the development of several chemoenzymatic approaches. Moreover, strained Ru(II) compounds have been shown to selectively inhibit P450 enzymes by releasing aromatic heterocycle containing molecules upon visible light excitation taking advantage of the rapid ligand loss feature in those complexes.

随着人们对利用可见光驱动生物催化过程的兴趣日益浓厚，已经采用了几种光捕获单元和方法来利用血红素单加氧酶的合成潜力并对各种底物进行选择性氧功能化。虽然细胞色素 P450 和 Ru(II) 光化学领域分别取得了丰富的成果，但直到 21 世纪之交它们才开始融合。非共价和随后共价连接的 Ru(II) 复合物用于促进细菌 P450 酶中的快速分子内电子转移。 Ru(II) 修饰的 P450 酶的光催化活性是在还原条件下通过明智地选择牺牲电子供体实现的。 Ru(II)修饰的P450酶的最初概念通过蛋白质工程、光敏剂功能化得到进一步改进，并成功应用于其他P450酶。在这篇综述中，我们希望介绍我们小组和其他人在光生物催化、蛋白质组装和化学酶反应的广泛背景下利用 Ru(II) 配合物与 P450 酶结合的最新贡献。化学催化剂与 P450 酶的合成潜力的结合导致了多种化学酶方法的发展。此外，应变Ru(II)化合物已被证明可以通过在可见光激发下释放含有芳香杂环的分子来选择性抑制P450酶，利用这些复合物中的快速配体损失特征。