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Synthesis of Ansa-[N]silacyclopentadienyl-Cycloheptatrienyl-Chromium Complexes (N = 1, 2): Novel Precursors for Polymers Bearing Chromium in the Backbone

Synthesis of Ansa-[N]silacyclopentadienyl-Cycloheptatrienyl-Chromium Complexes (N = 1, 2): Novel Precursors for Polymers Bearing Chromium in the Backbone

Alexandra Bartole-Scott, Holger Braunschweig, Thomas Kupfer, Matthias Lutz, Ian Manners, Thi-Loan Nguyen, Krzysztof Radacki, Fabian Seeler

Chemistry. 2006 Jan 23;12(4):1266-73.

PMID: 16281318

Abstract:

Reaction of [(eta5-C5H4Li)(eta7-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 [1]silatrochrocenophanes bearing Me2Si, (iPr)2Si, and silacyclobutane bridges revealed tilt angles alpha of 15.56(12) degrees , 15.8(1) degrees , and 16.33(17) degrees , respectively. Analogously, a [2]silatrochrocenophane (6) was prepared in excellent yield by reaction of [(eta5-C5H4Li)(eta7-C7H6Li)Cr]tmeda with 1,2-dichloro-1,1,2,2-tetramethyldisilane. This complex also was characterized structurally and exhibited a tilt angle alpha 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 [1]silatrochrocenophanes afforded ring-opened chromium-based polymers.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP814982	1,1,2,2-Tetramethyldisilane		814-98-2	Price

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