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Methandiide as a Non-Innocent Ligand in Carbene Complexes: From the Electronic Structure to Bond Activation Reactions and Cooperative Catalysis

机译:甲烷二胺作为碳络合物中的非纯配体:从电子结构到键活化反应和协同催化

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摘要

The synthesis of a ruthenium carbene complex based on a sulfonyl-substituted methandiide and its application in bond activation reactions and cooperative catalysis is reported. In the complex, the metal-carbon interaction can be tuned between a Ru-C single bond with additional electrostatic interactions and a Ru=C double bond, thus allowing the control of the stability and reactivity of the complex. Hence, activation of polar and non-polar bonds (O-H, H-H) as well as dehydrogenation reactions become possible. In these reactions the carbene acts as a non-innocent ligand supporting the bond activation as nucleophilic center in the 1,2-addition across the metal- carbon double bond. This metal-ligand cooperativity can be applied in the catalytic transfer hydrogenation for the reduction of ketones. This concept opens new ways for the application of carbene complexes in catalysis.
机译:报道了基于磺酰基取代的乙二胺的钌卡宾配合物的合成及其在键活化反应和协同催化中的应用。在该配合物中,可以在具有附加静电相互作用的Ru-C单键与Ru = C双键之间调节金属-碳相互作用,从而可以控制配合物的稳定性和反应性。因此,极性和非极性键(O-H,H-H)的活化以及脱氢反应变得可能。在这些反应中,卡宾充当非纯配体,在整个金属-碳双键的1,2-加成中支持键活化为亲核中心。这种金属-配体的协同作用可用于催化转移氢化中以还原酮。这一概念为卡宾络合物在催化中的应用开辟了新途径。

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