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A Stable Schrock-Type Hafnium−Silylene Complex

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Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
Cite this: J. Am. Chem. Soc. 2006, 128, 50, 16024–16025
Publication Date (Web):November 30, 2006
https://doi.org/10.1021/ja067251d
Copyright © 2006 American Chemical Society
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Abstract

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The first stable hafnium−silylene complex, (η-C5H4Et)2(PMe3)HfSi(SiMetBu2)2 (6) was obtained in the form of the phosphine adduct as red crystals by the coupling reaction of 1,1-dilithiosilane (1) with 0.9 equiv of (η-C5H4Et)2HfCl2 in dry toluene at −50 °C, followed by treatment with an excess of PMe3 at −50 °C. In the 29Si NMR spectrum of 6, the signal from the silylene ligand is shifted greatly downfield at 295.4 ppm, with a JSiP coupling constant of 15.0 Hz. X-ray crystallographic analysis of 6 revealed that the Si−Hf bond length (2.6515(9) Å) is about 5% shorter than typical Si−Hf single bonds, obviously indicating the double-bond character between the silicon and hafnium atoms. The compound 6 was found to be a Schrock-type silylene complex, a conclusion that was supported by the natural population analysis (NPA) charge distribution for the model complex, (η-C5H4Et)2(PMe3)HfSi(SiMe3)2 (8), showing a negative charge on the silicon atom (−0.34).

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The experimental procedures of 2−6, calculated geometries for 7 and 8, table of crystallographic data including atomic positional and thermal parameters for 6 (PDF/CIF). This material is available free of charge via the Internet at http://pubs.acs.org.

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This article is cited by 48 publications.

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