title: Methandiide as a non-innocent ligand in carbene complexes: from the electronic structure to bond activation reactions and cooperative catalysis.
abstract: 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.
authors.affiliation: Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany) http://www-anorganik.chemie.uni-wuerzburg.de/forschungsgruppen/dr_v_gessner/
authors.forename: Julia
authors.initials: J
authors.lastname: Becker
authors.forename: Tanja
authors.initials: T
authors.lastname: Modl
authors.forename: Viktoria H
authors.initials: VH
authors.lastname: Gessner
mesh_terms: D002384:Catalysis; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D004583:Electrons; D006865:Hydrogenation; D008024:Ligands; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008958:Models, Molecular; D012428:Ruthenium / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D008024:Ligands; C030011:carbene; D012428:Ruthenium; D008697:Methane
keywords: bond activation; carbene complexes; dianions; non-innocent ligands; transition metal catalysis