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Crystal structures of two ansa-titanocene tri-fluoro-methane-sulfonate complexes bearing the Me2Si(C5Me4)2 ligand

2016, Kessler, Monty, Godemann, Christian, Spannenberg, Anke, Beweries, Torsten

The crystal structures of two ansa-titanocene tri-fluoro-methane-sulfonate complexes bearing the Me2Si(C5Me4)2 ligand are reported, namely [di-methylbis-(η5-tetra-methyl-cyclo-penta-dien-yl)silane](tri-fluoro-methane-sulfonato-κ2O,O')titanium(III) toluene monosolvate, [Ti(CF3O3S)(C20H30Si)]·C7H8, 1, and chlorido-[di-methyl-bis-(η5-tetra-methyl-cyclo-penta-dien-yl)silane](tri-fluoro-methane-sulfonato-κO)titanium(IV), [Ti(CF3O3S)(C20H30Si)Cl], 2. Both complexes display a bent metallocene unit, the metal atom being coordinated in a distorted tetra-hedral geometry, with the tri-fluoro-methane-sulfonate anion acting as a bidentate or monodentate ligand in 1 and 2, respectively. In 1, weak π-π stacking inter-actions involving the toluene solvent mol-ecules [centroid-to-centroid distance = 3.9491 (11) Å] are observed.

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Highly selective visible light-induced Ti–O bond splitting in an ansa-titanocene dihydroxido complex

2015, Godemann, Christian, Dura, Laura, Hollmann, Dirk, Grabow, Kathleen, Bentrup, Ursula, Jiao, Haijun, Schulz, Axel, Brückner, Angelika, Beweries, Torsten

Irradiation of a substituted ansa-titanocene(IV) dihydroxido complex with visible light induces Ti–O bond dissociation. In contrast to previous studies on structurally similar unbridged complexes, no side reactions are observed and formation of the Ti(III) species is highly selective. The formation of OH radicals was proved using a biradicaloid species.