In this report we extend titanium-sulfide chemistry, describing the syntheses, structures, and chemistry of monocyclopentadienyl-titanium aryloxide sulfide complexes. Reduction of Cp'Ti(OC(6)H(3)-2,6-i-Pr(2))Cl(2) (Cp' = Cp (1), Cp (3)) with n-BuLi affords the Ti(III) compounds [CpTi(OC(6)H(3)-2,6-i-Pr(2))(&mgr;-Cl)](2) (2) and [CpTi(OC(6)H(3)-2,6-i-Pr(2))(&mgr;-Cl)](2) (4). Compound 2 is oxidized by moisture, giving [CpTi(OC(6)H(3)-2,6-i-Pr(2))Cl](2)(&mgr;-O) (5). Oxidation of 4 by sulfur led to a mixture of uncharacterized products; however, reaction of 3 with 2 equiv of n-BuLi followed by subsequent addition of sulfur afforded a new diamagnetic species, CpTi(OC(6)H(3)-2,6-i-Pr(2))S(5) (6). Oxidation of 2 by S(8) yields [CpTi(OC(6)H(3)-2,6-i-Pr(2))](2)(&mgr;-S)(&mgr;-S(2)) (7). Reaction of the known sulfide-bridged dimer [CpTi(OC(6)H(3)-2,6-i-Pr(2))(&mgr;-S)](2) (8) with sulfur provides an alternative route to 7. The conversion of 7 to 8 is reversible as reaction of 7 with PPh(3) yields SPPh(3) and 8 quantitatively. Reaction of 1 with Li(2)S proceeds cleanly to give 8. Reduction of CpTi(OC(6)H(3)-2,6-i-Pr(2))(SPh)Cl (9) with n-BuLi affords the diamagnetic product [CpTi(OC(6)H(3)-2,6-i-Pr(2))(&mgr;-SPh)](2) (10), which reacts with phenylpyridine to generate the paramagnetic species CpTi(OC(6)H(3)-2,6-i-Pr(2))(SPh)(NC(5)H(4)Ph) (11). Attempts to isolate a monosulfide-bridged complex are described. Isolation of a monosulfide-bridged species, [CpTi(OC(6)H(3)-2,6-i-Pr(2))(2)](2)(&mgr;-S) (14), is achieved via reaction of [CpTi(OC(6)H(3)-2,6-i-Pr(2))(2)Cl (13) with Li(2)S. Structural data for 2, 4-7, 10, and 14 are reported. Comparisons are made with the related titanocene-sulfide systems, and the implications are considered.
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Propylene polymerization to high molecular weight atactic polypropylene and copolymerization with 1-hexene using monocyclopentadienyl titanium catalysts.
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State Key Laboratory for Supramolecular Structure and Materials, School of Chemistry, Jilin University, 2699 Qianjin Street, Changchun, 130012, People's Republic of China.
A number of cyclopentadienyltitanium aryloxide complexes, 1-Ar-2,3,4,5-Me(4)-Cp(2,6-(i)Pr(2)C(6)H(3)O)TiCl(2) (Ar = 4-Me(3)SiPhenyl (5), 4-(i)PrPhenyl (6), 4-MePhenyl (7), 3,5-(CF(3))(2)Phenyl (8)) and (1-Ar-2,3,4,5-Me(4)CpTiCl(2))(2)(OAr'O) (Ar' = 4,4'-(3,3',5,5'-(i)Pr(4)C(6)H(2)-C(6)H(2)), Ar = 4-SiMe(3)Phenyl (9), 4-MePhenyl (10)) were synthesized from the reaction of a corresponding cyclopentadienyl titanium trichloride derivative with the lithium salt of a relevant phenol. The molecular structures of complexes 6, 7 and 8 were determined by X-ray crystallography. Upon activation with (i)Bu(3)Al and Ph(3)CB(C(6)F(5))(4), all mononuclear complexes 5-8 exhibit good catalytic activities for propylene polymerization, whereas the binuclear complexes 9 and 10 show lower catalytic activities under the same polymerization conditions.
View Article and Find Full Text PDFMonocyclopentadienyl-Titanium Aryloxide Sulfide Complexes.
Inorg Chem
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Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ontario, Canada N9B 3P4.
In this report we extend titanium-sulfide chemistry, describing the syntheses, structures, and chemistry of monocyclopentadienyl-titanium aryloxide sulfide complexes. Reduction of Cp'Ti(OC(6)H(3)-2,6-i-Pr(2))Cl(2) (Cp' = Cp (1), Cp (3)) with n-BuLi affords the Ti(III) compounds [CpTi(OC(6)H(3)-2,6-i-Pr(2))(&mgr;-Cl)](2) (2) and [CpTi(OC(6)H(3)-2,6-i-Pr(2))(&mgr;-Cl)](2) (4). Compound 2 is oxidized by moisture, giving [CpTi(OC(6)H(3)-2,6-i-Pr(2))Cl](2)(&mgr;-O) (5).
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