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Novel Ruthenium Dihydrogen Complexes and their Application in Catalysis

MPG-Autoren
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Prechtl,  Martin H. G.
Service Department Leitner (Technical Labs), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Zitation

Prechtl, M. H. G. (2007). Novel Ruthenium Dihydrogen Complexes and their Application in Catalysis. PhD Thesis, Rheinisch-Westfälische Technische Hochschule, Aachen.


Zitierlink: https://hdl.handle.net/11858/00-001M-0000-000F-92A5-5
Zusammenfassung
The synthesis of the non-classical ruthenium dihydrogen complexes [Ru(dtbpmp)H2(H2)] (PNP-pincer backbone) and [Ru(dtbpoet)(H2)H2] (POP-pincer backbone) with constrained geometries, their application in homogeneous catalysis and their reactivity towards small molecules like N2, CO2 and CO is described. The complexes with side-on bonded molecular hydrogen were analysed by NMR (T1-analysis), FT-IR and by means of DFT calculations. Ruthenium dihydrogen complexes have a great potential as catalysts for CH-activation, especially for H/D-exchange and hydrogen transfer processes. We successfully generated a ruthenium hydride catalyst for the H/D-exchange between (hetero)aromatic or olefinic protons and D2O (or C6D6) under mild conditions. The H/D-exchange processes included mechanistic investigation (NMR- kinetics and DFT calculations). Interestingly, it is also catalytically active in acceptorless dehydrogenation of alcohols to esters and some other reactions.