TITANIUM COMPLEXES OF CHELATING BIS(PHENOLATO) LIGANDS WITH LONG TITANIUM-SULFUR BONDS - A NOVEL TYPE OF ANCILLARY LIGAND FOR OLEFIN POLYMERIZATION CATALYSTS

The sulfide-linked bis(phenol) tbmpH(2) (tbmp = 2,2'-thiobis(6-tert-bu tyl-4-methylphenolato)) gives a series of titanium complexes of the fo rmula [Ti(tbmp)X(2)](2) or [Ti(tbmp)(L)X(2)] (L = true-electron ligand , X = one-electron ligand). The molecular structures of [Ti(tbmp)(OiPr )(2)](2) and of [Ti(tbmp){C6H4(CH(2)NMe(2))-2}Cl] were determined by s ingle-crystal X-ray structural analyses. An unusually long titanium-su lfur bond of similar to 270 pm is observed in. both complexes which co ntain a six-coordinate titanium center. Variable-temperature NMR spect roscopy shows a fluxional coordination of the chelating aryl group in [Ti(tbmp){C6H4(CH(2)NMe(2))-2}Cl].