期刊
ORGANOMETALLICS
卷 28, 期 2, 页码 499-505出版社
AMER CHEMICAL SOC
DOI: 10.1021/om800717h
关键词
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资金
- National Natural Science Foundation of China [20671021]
Reaction of titanium complex [(L)TiX(2)(THF)] (L = (N,N'-[(5-R-3-tert-Bu-2-O(-)-C(6)H(2))CH(2)](2) (C(3)H(2)N(2))}, R = tert-Bu, L(a), R = Me, L(b); X = Cl, 1a, 1b; X = Br, L(a), 2) with 2.0 equiv of PhCH(2)MgCl or MeLi in diethyl ether gave dimethyl complexes [(L)Ti(CH(2)Ph)(2)] (3a, 3b) and [(L)Ti(CH(3))(2)](4a, 4b) by salt metathesis. Dibenzyl titanium complex [(L(a))Ti(CH(2)Ph)(2)] (3a) absorbs dioxygen gas to afford the oxygeninsertion product [(L(a))Ti(OCH(2)Ph)(2)] (5) in 57% yield. The reduction of [(L(a))MBr(2)(THF)] (2) with 1 equiv of LiBEt(3)H in toluene gave the titanium(III) species [(L(a))TiBr(THF)(2)] (6). The molecular structures of 3b, 4b, 5, and 6 have been confirmed by X-ray single-crystal analysis. The solid state structures of these compounds reveal that these hybrid carbene ligands adopt a transoid conformation to form a pseudotrigonal-bipyramidal (for 3b, 4a, 4b, and 5) or octahedral (for 6) coordination geometry around metal centers. These titanium complexes (1, 2, and 6) showed high activities up to ca. 97 kg PE/(mol Ti center dot h center dot atm) for ethylene polymerization in the presence of MAO as coactalyst. The (13)C NMR analysis revealed that linear polyethylene with low molecular weight was formed by these NBC titanium complexes. No methyl or other long-chain branch could be observed.
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