Kurzbeschreibung
(Englisch)
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Classical and nonclassical carbene-pyridine C,N coordinating ligand systems, both developed previously in our laboratories, will be functionalized by anellation of metallocenes. This approach offers outstanding opportunities to tune the pielectron density at the ligand and hence also at the metal center, which will have a pronounced effect on metal-mediated hydrogenation catalysis: 1) Activity: the new degree of pi-tunability through the metallocene provides a new methodology to optimize oxidative H–H activation at the metal center and reductive R3C–H elimination, both key steps of the catalytic hydrogenation cycle. 2) Selectivity: the anellated metallocene induced planar asymmetry. This will be exploited in enantioselective hydrogen transfer reactions and also in direct hydrogenation in close cooperation with Prof. Gladiali. At a later stage, this approach will be extended to different reactions such as (asymmetric) C–C bond formation in collaboration with Prof. Claver.
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Partner und Internationale Organisationen
(Englisch)
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AT, BE, CH, DE, DK, ES, FI, FR, GR, HU, IE, IT, LT, MT, NL, PL, PT, RO, SE, SI, SK, TR, UK
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Abstract
(Englisch)
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Classical and nonclassical carbene-pyridine C,N coordinating ligand systems, both developed previously in our laboratories, will be functionalized by anellation of metallocenes. This approach offers outstanding opportunities to tune the pielectron density at the ligand and hence also at the metal center, which will have a pronounced effect on metal-mediated hydrogenation catalysis: 1) Activity: the new degree of pi-tunability through the metallocene provides a new methodology to optimize oxidative H–H activation at the metal center and reductive R3C–H elimination, both key steps of the catalytic hydrogenation cycle. 2) Selectivity: the anellated metallocene induced planar asymmetry. This will be exploited in enantioselective hydrogen transfer reactions and also in direct hydrogenation in close cooperation with Prof. Gladiali.
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