Synthesis of ansa-[n]silacyclopentadienyl-cycloheptatrienyl-chromium complexes (n=1,2):: Novel precursors for polymers bearing chromium in the backbone

被引：64

作者：

Bartole-Scott, A

Braunschweig, H ^{[1
]}

Kupfer, T

Lutz, M

Manners, I

Nguyen, TL

Radacki, K

Seeler, F

机构：

[1] Univ Wurzburg, Inst Anorgan Chem, D-97074 Wurzburg, Germany

[2] Univ Toronto, Dept Chem, Toronto, ON M5S 3H6, Canada

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2006年 / 12卷 / 04期

关键词：

ansa-silametallocenes; chromium; metallocenes; metallopolymers; oxidative addition; ring-opening polymerization; silicon;

D O I：

10.1002/chem.200500689

中图分类号：

O6 [化学];

学科分类号：

0703 [化学];

摘要：

Reaction of [(eta(5)-C5H4Li)(eta(7)- C7H6Li)Cr]-tmeda with a variety of dialkyl(dichloro)silanes in aliphatic solvents afforded the corresponding [1]silatrochrocenophanes. Structural characterization by X-ray diffraction analysis of the [I.]silatrochrocenophanes bearing Me2Si, (iPr)(2)Si, and silacyclobutane bridges revealed tilt angles a of 15.56(12)degrees, 15.8(1)degrees, and 16.33(17)degrees, respectively. Analogously, a [2]silatro-chrocenophane (6) was prepared in excellent yield by reaction of [(eta(5)- C5H4Li) (eta(7)-C7H6Li)Cr]-tmeda with 1,2-dichloro-1,1,2,2-tetramethyldisilane. This complex also was characterized structurally and exhibited a tilt angle a of 2.60(15)degrees. The [1]silatrochrocenophane bearing the Me2Si bridge underwent facile and regioselective carbon-silicon bond cleavage with [Pt(PEt3)(4)] to give a very high yield of an oxidative addition product. The ring-opening polymerization of these novel [I]silatrochrocenophanes afforded ring-opened chromium-based polymers.

引用

页码：1266 / 1273

页数：8

共 53 条

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