In:
Chemistry – A European Journal, Wiley, Vol. 19, No. 41 ( 2013-10-04), p. 13705-13713
Abstract:
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 H 2 O molecules coordinate to [Cp* 2 Ti III (OTf)] subsequently forming [Cp 2 *Ti III (H 2 O)(OTf)] and [Cp*Ti III (H 2 O) 2 (OTf)]. Triflate stabilizes the water ligands by hydrogen bonding. Liberation of hydrogen proceeds only from the diaqua complex [Cp*Ti III (H 2 O) 2 (OTf)] and involves, most probably, abstraction and recombination of two H atoms from two molecules of [Cp*Ti III (H 2 O) 2 (OTf)] in close vicinity, which is driven by the formation of a strong covalent TiOH bond in the resulting final product [Cp* 2 Ti IV (OTf)(OH)].
Type of Medium:
Online Resource
ISSN:
0947-6539
,
1521-3765
DOI:
10.1002/chem.201301598
Language:
English
Publisher:
Wiley
Publication Date:
2013
detail.hit.zdb_id:
1478547-X
detail.hit.zdb_id:
1231884-X