Methandiide as a Non-Innocent Ligand in Carbene Complexes: From the Electronic Structure to Bond Activation Reactions and Cooperative Catalysis
Methandiide as a Non-Innocent Ligand in Carbene Complexes: From the Electronic Structure to Bond Activation Reactions and Cooperative Catalysis
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DOI：
10.1002/chem.201404131
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发表时间：
2014-09-01
影响因子：
4.3
通讯作者：
Gessner, Viktoria H.
中科院分区：
文献类型：
--
作者：
Becker, Julia;Modl, Tanja;Gessner, Viktoria H.
报道了一种磺酰基取代甲烷二亚胺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。在配合物中，金属-碳相互作用可以在具有额外静电相互作用的Ru-C单键和Ru=C双键之间进行调节，从而允许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成为可能。在这些反应中，卡宾作为非无辜配体支持键活化，作为跨金属-碳双键的1，2-加成中的亲核中心。这种金属-配体协同作用可应用于酮的催化转移氢化反应。这一概念为卡宾配合物在催化中的应用开辟了新的途径。
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.