The reaction of methyl-4,6-O-(naphthyl-2'-methylidene)-alpha-D-glucopyranoside (alpha-MeNGH(2)) with trichloridopentamethylcyclopentadienyltitanium {[}Cp{*}TiCl3] and triethylamine in toluene reveals the dinuclear complex {[}(Cp{*}TiCl)-mu-(alpha-MeNG)](2) (2). Complex 2 was characterized by elemental analysis, H-1 and C-13 NMR spectroscopy, circular dichroism, as well as single-crystal structure analysis. Compared to the complex with the beta-anomer of the ligand in {[}(Cp{*}TiCl)-mu-(beta-MeNG)](2) (1), it is obvious that the absolute configuration of the Ti atoms in 2 have changed. ((C) Wiley-VCH Verlag GmbH \& Co. KGaA, 69451 Weinheim, Germany, 2009)