Abstract
Two ligand exchange reactions at the titanium atom in quasi-tetrahedral titanocene complexes have been studied. The first is substitution of a Cl ligand by an aryloxy group starting from substrates η 5-Cp-η 5-Cp′Ti(Cl)OPh which have an planar chirality on the Cp′ ring. The second is the substitution of one of the aryloxy groups of the complexes η 5-Cp-η 5-Cp′Ti(OPh′)OPh by the action of HCl. In this case, the reaction is generally selective and has a high degree of stereo-specificity with retention at the titanium atom. This retention has been established by crystallographic analysis of two suitable substrates: diastereoisomer F. 171°C of η 5-C 5H 5[η 5-(1-Me-3-CHMe 2C 5H 5)](2-ClC 6H 4O)(2,6-Me 2C 6H 3O)Ti and diastereoisomer F. 134°C of η 5-C 5H 5[η 5-(1-Me-3-CHMe 2C 5H 3)](2-ClC 6H 4O)TiCl.
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