Cooperative multimetallic catalysis is a fascinating field of research further expanding the role of homogeneous catalysis. The simultaneous activation of two substrates or functionalities by different catalytic entities and their subsequent coupling are the responsible for the rate acceleration and selectivity exerted by these systems. The nature of the metal moieties is the responsible of the activation step, while selectivity mainly derives from supramolecular interactions between the substrates and the catalysts, particularly during coupling. The control of both activation and coupling opens the way for the design of new highly selective synthetic routes proceeding in mild conditions. Molecular modelling is becoming nowadays an essential tool in rational design of metal-mediated catalysis. Theoretical models provide fundamental insights on the substrate activation by metals as well as on the interactions between the different catalysts. This can allow the deciphering at the atomic level of the preferential pathways leading to different reaction products. In this contribution, we discuss a series of representative examples of multimetallic cooperative processes described by means of molecular modelling.

协同多金属催化是一个引人入胜的研究领域，进一步扩展了均相催化的作用。不同催化实体同时激活两种底物或官能团及其随后的偶联是这些系统发挥速率加速和选择性的原因。金属部分的性质决定了活化步骤，而选择性主要来自底物和催化剂之间的超分子相互作用，特别是在偶联过程中。活化和偶联的控制为设计在温和条件下进行的新的高选择性合成路线开辟了道路。如今，分子建模正成为合理设计金属介导催化的重要工具。理论模型为金属对底物的活化以及不同催化剂之间的相互作用提供了基本见解。这可以允许在原子水平上破译导致不同反应产物的优先途径。在这篇文章中，我们讨论了一系列通过分子建模描述的多金属协同过程的代表性例子。