title: Synthesis and structures of ansa-titanocene complexes with diatomic bridging units for overall water splitting.
abstract: The synthesis of a series of ansa-titanocene dichlorides [Cp'2TiCl2] (Cp' = bridged η(5)-tetramethylcyclopentadienyl) and the corresponding titanocene bis(trimethylsilyl)acetylene complexes [Cp'2Ti(η(2)-Me3SiC2SiMe3)] is described. The ethanediyl-bridged complexes [C2H4(C5Me4)2TiCl2] (2-Cl2) and [C2H4(C5Me4)2Ti(η(2)-Me3SiC2SiMe3)] (2-btmsa; btmsa = η(2)-Me3SiC2SiMe3) can be obtained from the hitherto unknown calcocenophane complex [C2H4(C5Me4)2Ca(THF)2] (1). Furthermore, a heterodiatomic bridging unit containing both, a dimethylsilyl and a methylene group was introduced to yield the ansa-titanocene dichloride [Me2SiCH2(C5Me4)2TiCl2] (3-Cl2) and the bis(trimethylsilyl)acetylene complex [Me2SiCH2(C5Me4)2Ti(η(2)-Me3SiC2SiMe3)] (3-btmsa). Besides, tetramethyldisilyl- and dimethylsilyl-bridged metallocene complexes (structural motif 4 and 5, respectively) were prepared. All ansa-titanocene alkyne complexes were reacted with stoichiometric amounts of water; the hydrolysis products were isolated as model complexes for the investigation of the elemental steps of overall water splitting. Compounds 1, 2-btmsa, 2-(OH)2, 3-Cl2, 3-btmsa, 4-(OH)2, 3-alkenyl and 5-alkenyl were characterised by X-ray diffraction analysis.
authors.affiliation: Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany.
authors.forename: Monty
authors.initials: M
authors.lastname: Kessler
authors.forename: Sven
authors.initials: S
authors.lastname: Hansen
authors.forename: Christian
authors.initials: C
authors.lastname: Godemann
authors.forename: Anke
authors.initials: A
authors.lastname: Spannenberg
authors.forename: Torsten
authors.initials: T
authors.lastname: Beweries
mesh_terms: D000818:Animals; D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D017646:Organosilicon Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D014867:Water / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D017646:Organosilicon Compounds; C013108:metallocene; D014867:Water; C406884:titanocene; C020528:titanocene dichloride