Department of Chemistry, University of California Irvine, Irvine, California 92697-2025, USA.
Dalton Trans. 2013 Mar 21;42(11):3751-66. doi: 10.1039/c2dt32063k. Epub 2013 Jan 18.
Group- and atom-transfer is an attractive reaction class for the preparation of value-added organic substrates. Despite a wide variety of known early-transition metal oxo and imido complexes, these species have received limited attention for atom- and group-transfer reactions, owing to the lack of an accessible metal-based two-electron redox couple. Recently it has been shown that redox-active ligands can support the multi-electron changes required to promote group-transfer reactivity, opening up new avenues for group- and atom-transfer catalyst design. This Perspective article provides an overview of group transfer reactivity in early-transition metal complexes supported by traditional ligand platforms, followed by recent advances in the atom- and group-transfer reactivity of d(0) metal complexes containing redox-active ligands.
基团转移和原子转移是制备增值有机底物的一种有吸引力的反应类型。尽管已知有各种各样的早期过渡金属氧和亚胺配合物，但由于缺乏可及的基于金属的两电子氧化还原对，这些物种在原子和基团转移反应中受到的关注有限。最近表明，氧化还原活性配体可以支持促进基团转移反应所需的多电子变化，为基团转移和原子转移催化剂设计开辟了新途径。本文综述了传统配体平台支持的早期过渡金属配合物的基团转移反应性，然后介绍了含氧化还原活性配体的 d(0)金属配合物的原子和基团转移反应性的最新进展。
