Abstract: | Syntheses and Structures of the Titanium(III) Siloxanes Ti(OSiPh3)3(thf)2] and Ti(OSiPh3)3(py)2] The new titaniumtrioxysilanes Ti(OSiPh3)3(thf)2] ( 1 ) and Ti(OSiPh3)3(py)2] ( 2 ) have been obtained from the reaction of titaniumtrichloride with LiOSiPh3 in the presence of the corresponding bases tetrahydrofurane (thf) and pyridine (py). From the crystal structures of both compounds it is evident that the titanium atoms are in the centres of trigonal‐bipyramidal coordination figures, with the donor atoms in axial positions. The compounds 1 and 2 have slightly different structures (mean values: 1 : Ti‐O(Si) 1.897(9), Ti‐O(C) 2.136(8) Å; 2 : Ti‐O 1.902(9), Ti‐N2.252(8) Å) and have a single absorption band in the visible region of the UV‐spectrum. The exchange of the thf‐ligands in 1 by pyridine (in high molar excess) seems to be hindered as deduced from UV‐spectroscopy. |