Electron-Deficient Group 4 Metal Complexes of Sulfur-Bridged Dialkoxide Ligands: Synthesis, Structure, and Polymerization Activity Studies

Coordination of the sulfur-bridged dialkoxide ligands {OCR2CH2SCH2CR2O}2- ({OSOR}2-, R = Me, p-tolyl) on titanium and zirconium centers has been studied. A variety of complexes having one or two ancillary {OSOMe}2- ligands, viz., M(OR)2{OSOMe} (M = Zr, OR = OtBu, 4; M = Ti, OR = OiPr, 5), M{OSOMe}2 (M = Zr, 6; Ti, 7), Zr(CH2Ph)2{OSOMe} (8), and MCl2{OSOMe}(THF)n (M = Zr, n = 0, 9; n = 1, 10; n = 2, 11; M = Ti, n = 0, 12; n = 2, 13), have been prepared in good yields by alcohol or alkane elimination from {OSOMe}H2 (1a) or by salt metathesis routes from alkali metal salts M{OSOMe} (M = K, 2a; M = Li, in situ-generated). Coordination of the p-tolyl-substituted ligand by these and other routes proved to be much more difficult, and only TiCl2{OSOtol} (14) was obtained. Crystallographic studies showed that dichloro complexes 11 and 13 and bis-ligand complex 7 adopt in the solid state mononuclear structures with no bonding interaction between the sulfur atom and metal centers. The crystal structure of 4 contains...

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