Alkylidene-Ruthenium-Tin Catalysts for the Formation of Fatty Nitriles and Esters via Cross-Metathesis of Plant Oil Derivatives
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- 作者：Xiaowei Miao ; Anton Blokhin ; Alexandr Pasynskii ; Sergey Nefedov ; Sergey N. Osipov ; Thierry Roisnel ; Christian Bruneau ; Pierre H. Dixneuf
- 刊名：Organometallics
- 出版年：2010
- 出版时间：November 8, 2010
- 年：2010
- 卷：29
- 期：21
- 页码：5257-5262
- 全文大小：890K
- 年卷期：v.29,no.21(November 8, 2010)
- ISSN：1520-6041
文摘
The reaction of SnCl2 with the Ru−Cl bond of the Grubbs I catalyst RuCl2(═CHPh)(PCy3)2 (1) gives the complex {[Ru(═CHPh)(SnCl3)(PCy3)]2(μ-Cl)3}−[HPCy3]+ (2), but containing two diethyl ether solvate molecules. The formal insertion of SnCl2 into one Ru−Cl bond of the Hoveyda II catalyst RuCl2(═CH-C6H4OPri)(H2IMes) (3) (H2IMes = N,N′-dimesityl-4,5-dihydroimidazol-2-ylidene) results in formation of the new complex RuCl(SnCl3)(═CH-C6H4OPri)(H2IMes) (4). The X-ray analyses of 2 and 4 show the presence of very short Ru−Sn bonds (2.5834(9) Å mean bond for 2 and 2.5925(12) Å for 4) and the retention of short Ru═C bonds (1.895(10) and 1.825(8) Å, respectively). Complex 4 shows an excellent catalytic activity for the cross-metathesis of plant oil derivatives, the C11 ω-unsaturated ester and aldehyde and the unsaturated C18 diester with acrylonitrile, and a good activity for their cross-metathesis with methyl acrylate. Good to excellent yield of α,ω-bifunctional compounds, precursors of polyesters and polyamides, were obtained. Complex 2 shows catalytic activity for the self-metathesis of C11 ω-unsaturated aldehyde at low concentration to produce C20 α,ω-dialdehyde.