ISSN:
0009-2940
Keywords:
Substituted metallocene complexes
;
N-Functionalized cyclopentadienyl ligands
;
Ethylene polymerization
;
Dehydrocoupling of phenylsilane
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Mixed bent sandwich titanium (IV) complexes containing the donor-substituted [2-(diisopropylamino)ethyl]cyclopentadienyl (C5H4CH2CH2NiPr2 ≡ CpN) ligand are described. The highly moisture-sensitive metallocene dichloride (C5H4CH2CH2NNiPr2)(C5H4SiMe3)TiCl2 (1) was synthesized by reaction of CpNLi with CpSTiCl3 (CpS ≡ C5H4SiMe3). Complex 1 reacts with one equivalent of HCl with protonation of the amino group to give the air- and water-stable metallocene dichloride-hydrochloride [(C5H4CH2CH2-N(H)iPr2)(C5H4SiMe3)TiCl2]+Cl- (2). The structure of 2 was determined by a single-crystal X-ray diffraction study. Compounds 1 and 2 are precursors for ethylene polymerization catalysts. The reaction of 2 with one equivalent of Na+B[3,5-(CF3)2C6H3]4- afforded the borate [(C5H4CH2CH2N(H)iPr2)-(C5H4SiMe3)TiCl2]+B[3,5-(CF3)2C6H3]4- (3). The dimethyl compounds (C5H4CH2CH2NiPr2)(C5H4SiMe3)Time2 (4) was obtained by reaction of 1 with two equivalents of methyllithium. The diphenoxy complex (C5H4CH2CH2-NiPr2)(C5H4SiMe3)Ti(OPh)2 (5) was prepared analogously with a stoichiometric amount of lithium phenoxide. Compounds 4 and 5 show remarkable activity in the catalytic dehydrocoupling of phenylsilane.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19961291218
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