Titanium complexes based on the (R,R)-N,N ' -bis(2-hydroxy-3-functionalised-benzylidene)-1,2-diaminocyclohexa ne ligand and containing either chloro or bridged oxo co-ligands have been prepared, subjected to single crystal X-ray analysis and examined as pre-catalysts for the asymmetric phospho-aldol (PA) reaction. Catalysis does take place although at a much slower rate than with related aluminium complexes and then only to afford racemic products; significant observations that lead to an important design point in PA pre-catalysts.