Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 19, Issue 41, Pages 13705-13713Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201301598
Keywords
density functional calculations; EPR spectroscopy; hydrogen production; IR spectroscopy; titanium; water activation
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Funding
- State of Mecklenburg-Vorpommern
- BMBF
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A detailed mechanism of hydrogen production by reduction of water with decamethyltitanocene triflate [Cp*Ti-2(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 H2O molecules coordinate to [Cp*Ti-2(III)(OTf)] subsequently forming [Cp-2*Ti-III(H2O)(OTf)] and [Cp*Ti-III(H2O)(2)(OTf)]. Triflate stabilizes the water ligands by hydrogen bonding. Liberation of hydrogen proceeds only from the diaqua complex [Cp*Ti-III(H2O)(2)(OTf)] and involves, most probably, abstraction and recombination of two H atoms from two molecules of [Cp*Ti-III(H2O)(2)(OTf)] in close vicinity, which is driven by the formation of a strong covalent TiOH bond in the resulting final product [Cp*Ti-2(IV)(OTf)(OH)].
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