Hydrogen Generation by Water Reduction with [Cp*2Ti(OTf)]: Identifying Elemental Mechanistic Steps by Combined In Situ FTIR and In Situ EPR Spectroscopy Supported by DFT Calculations

Autor:	Torsten Beweries, Haijun Jiao, Kathleen Grabow, Dirk Hollmann, Anke Spannenberg, Ursula Bentrup, Monty Kessler, Angelika Brückner
Rok vydání:	2013
Předmět:	Hydrogen Chemistry Hydrogen bond Organic Chemistry Infrared spectroscopy chemistry.chemical_element General Chemistry Photochemistry Catalysis law.invention law Covalent bond Physical chemistry Molecule Electron paramagnetic resonance Spectroscopy Trifluoromethanesulfonate
Zdroj:	Chemistry - A European Journal. 19:13705-13713
ISSN:	0947-6539
Popis:	A detailed mechanism of hydrogen production by reduction of water with decamethyltitanocene triflate [Cp*2 Ti(III) (OTf)] has been derived for the first time, based on a comprehensive in situ spectroscopic study including EPR and ATR-FTIR spectroscopy supported by DFT calculations. It is demonstrated that two H2 O molecules coordinate to [Cp*2 Ti(III) (OTf)] subsequently forming [Cp2 *Ti(III) (H2 O)(OTf)] and [Cp*Ti(III) (H2 O)2 (OTf)]. Triflate stabilizes the water ligands by hydrogen bonding. Liberation of hydrogen proceeds only from the diaqua complex [Cp*Ti(III) (H2 O)2 (OTf)] and involves, most probably, abstraction and recombination of two H atoms from two molecules of [Cp*Ti(III) (H2 O)2 (OTf)] in close vicinity, which is driven by the formation of a strong covalent TiOH bond in the resulting final product [Cp*2 Ti(IV) (OTf)(OH)].
Databáze:	OpenAIRE
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