α- and β-Agostic Alkyl-Titanocene Complexes

被引：26

作者：

Dunlop-Briere, Alexandre F. ^{[2
]}

Budzelaar, Peter H. M. ^{[1
]}

Baird, Michael C. ^{[2
]}

机构：

[1] Univ Manitoba, Dept Chem, Winnipeg, MB R3T 2N2, Canada

[2] Queens Univ, Dept Chem, Kingston, ON K7L 3N6, Canada

来源：

ORGANOMETALLICS | 2012年 / 31卷 / 05期

基金：

加拿大创新基金会;

关键词：

CATALYZED OLEFIN POLYMERIZATION; ETHYLTITANIUM TRICHLORIDE; METALLOCENE COMPLEXES; ALKENE POLYMERIZATION; CRYSTAL-STRUCTURES; ZIRCONOCENE; CHEMISTRY; DISSOCIATION; INSERTION; TITANIUM;

D O I：

10.1021/om3001197

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction of [Cp2Ti(Me)(CD2Cl2)](+) (I) with 3,3-dimethyl-1-butene in oCD(2)Cl(2) at 205 K produces the alpha-agostic insertion product [(Cp2TiCH2CHMeBu)-Bu-t](+) (II), in which the chirality at C(2) induces preferential agostic binding of one of the diastereotopic alpha-H atoms; subsequent coordination of ethyl ether to II leaves the alpha-agostic interaction weakened but intact. On warming, II undergoes beta-hydrogen elimination and the resulting hydride reacts further with excess 3,3-dimethyl-1-butene to form the beta-agostic species [(Cp2TiCH2CH2Bu)-Bu-t](+). NMR data and calculated (DFT) energies support the assignments.

引用

页码：1591 / 1594

页数：4

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