Synthesis and Characterizations of Ti(O‐i‐Pr)Cl3(THF)(PhCOR) (R = H,Me, Ph) and Ti(O‐i‐Pr)Cl3(PhCOR)2 (R = Me,Ph). The Molecular Structure of Ti(O‐i‐Pr)Cl3(PhCOPh)2

A series of titanium(IV) complexes Ti(O‐i‐Pr)Cl₃(THF)(PhCOR) (R = H ( 1 ), CH₃ ( 2 ), or Ph ( 3 )) is prepared quantitatively from reactions of Ti(O‐i‐Pr)Cl₂(THF)(μ‐Cl)]₂ with 2 molar equiv. PhCOR. Treatment of Ti(O‐i‐Pr)Cl₃ with 2 molar equiv. of PhCOR affords the disubstituted complexes Ti(O‐i‐Pr)Cl₃(PhCOR)₂ (R = CH₃ ( 4 ) or Ph ( 5 )). The ¹³C NMR study of these complexes shows that the relative bonding abilities are in the order of PhCOCH₃ > PhCHO > PhCOPh. The molecular structure of 5 reveals that one of the benzophenone ligands is trans to the strongest 2‐propoxide ligand with a long Ti‐O(carbonyl) distance of 2.193(5) Å which is much longer than the other Ti‐O(carbonyl) distance of 2.097(4) Å by ?0.1 Å. All ligands cis to the alkoxide ligand are bending away from the alkoxide ligand with the RO‐Ti‐L angles ranging from 93.6(2) to 99.0(2)°.