Metal-Ligand Cooperation
Metal-Ligand Cooperation
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DOI：
10.1002/anie.201503873
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发表时间：
2015-10-12
影响因子：
16.6
通讯作者：
Milstein, David
中科院分区：
文献类型：
--
作者：
Khusnutdinova, Julia R.;Milstein, David
金属-配体协同作用（MLC）已成为过渡金属配合物在合成和生物体系中催化作用的重要概念。MLC意味着金属和配体都直接参与键活化过程，与“经典”过渡金属催化相反，在“经典”过渡金属催化中，配体（例如膦）充当旁观者，而所有关键转化都发生在金属中心。在这篇综述中，我们将讨论MLC的例子，其中1）在键活化过程中金属和配体都被化学修饰，2）键活化导致涉及配合配体的第一配位球立即发生变化，即使配体的反应中心不直接与金属结合（例如通过互变异构）。MLC的作用，使有效的催化，以及在催化剂失活反应将进行讨论。
Metal-ligand cooperation (MLC) has become an important concept in catalysis by transition metal complexes both in synthetic and biological systems. MLC implies that both the metal and the ligand are directly involved in bond activation processes, by contrast to "classical" transition metal catalysis where the ligand (e.g. phosphine) acts as a spectator, while all key transformations occur at the metal center. In this Review, we will discuss examples of MLC in which 1) both the metal and the ligand are chemically modified during bond activation and 2) bond activation results in immediate changes in the 1st coordination sphere involving the cooperating ligand, even if the reactive center at the ligand is not directly bound to the metal (e.g. via tautomerization). The role of MLC in enabling effective catalysis as well as in catalyst deactivation reactions will be discussed.