Palladium and Platinum Silyl Complexes as Reactive Intermediates for the Catalytic Hydrogenolysis of Disilanes


The research project involves the development of a homogeneous catalytic process for the hydrogenolysis of disilanes with H2. The elementary steps of a putative catalytic cycle will be investigated by model reactions. After an oxidative addition of disilanes at neutral complexes, a hydrogenolysis of the metal-silicon bond will be studied. Cationic silyl complexes, which possess a free coordination site, will also be synthesized. Mechanistically oxidative addition reactions, reductive eliminations or o-bond metathesis reactions may play a certain role. We will try to detect intermediates by low temperature IR, Raman and NMR spectroscopy. Based on the model reactions a new catalytic cycle for the transition metal mediated hydrogenolysis of disilanes will be developed.
The research project involves the development of a homogeneous catalytic process for the hydrogenolysis of disilanes with H2. The elementary steps of a putative catalytic cycle will be investigated by model reactions. After an oxidative addition of disilanes at neutral complexes, a hydrogenolysis of the metal-silicon bond will be studied. Cationic silyl complexes, which possess a free coordination site, will also be synthesized. Mechanistically oxidative addition reactions, reductive eliminations or o-bond metathesis reactions may play a certain role. We will try to detect intermediates by low temperature IR, Raman and NMR spectroscopy. Based on the model reactions a new catalytic cycle for the transition metal mediated hydrogenolysis of disilanes will be developed.


Principal Investigators
Braun, Thomas Prof. Dr. (Details) (Inorganic Chemistry)

Duration of Project
Start date: 11/2009
End date: 10/2013

Research Areas
Anorganische Chemie

Publications
J. Voigt, T. Braun, Dalton Trans. 2011, 40, 12699-12704.
"Si–H and Si–Si activation at Pt: synthesis and reactivity of neutral and cationic silyl complexes"

J. Voigt, M. Chilleck, T. Braun, Dalton Trans. 2013, 42, 4052-4058.
"Activation of Si–Si and Si–H bonds at Pt: a catalytic hydrogenolysis of silicon–silicon bonds "

C. Mitzenheim, T. Braun, Angew. Chem. 2013, 125, 8787-8790; Angew. Chem. Int. Ed. 2013, 52, 8625-8628.
"Si-Si and Si-O Bond Activation at Platinum: Stepwise Formation of a SiH3 Complex"

Last updated on 2020-03-12 at 16:43