Synthesis and Characterisation of Various Diester and Triester Adducts of TiCl 4

Titanium(IV) chloride and the triester glycerol tribenzoate (gtb) were reacted under moisture‐free conditions in order to investigate the use of triester‐containing oils in the purification of TiCl 4 in industrial processes. This resulted in the isolation of a chloro‐bridged dimeric complex containing four titanium centres [{(TiCl 4 ) 2 (gtb)} 2 ] ( 1 ). Further novel coordination compounds of TiCl 4 and the diesters; diisopropyl malonate, dibenzyl malonate and diethyl succinate were synthesised by direct reaction under moisture‐free conditions, yielding [TiCl 4 {CH 2 (COO i Pr) 2 }] ( 2 ), [TiCl 4 {CH 2 (COOCH 2 Ph) 2 }] ( 3 ) and [TiCl 4 {C 2 H 4 (COOEt) 2 }] ( 4 ) respectively. The structures of compounds 1 – 4 were determined by single‐crystal X‐ray diffraction. All structures assumed an octahedral geometry consisting of the titanium bound to four chloride ligands and the diester molecule acting as a bidentate ligand, through its two carbonyl oxygen atoms. Exposure of the isopropyl malonate reaction to trace amounts of water during synthesis resulted in the formation of an oxo‐bridged dimeric structure [Ti 2 (μ‐O)Cl 3 {CH 2 (COO i Pr) 2 } 2 ] ( 2b ), the structure of which was also obtained via single‐crystal X‐ray diffraction.