Alkylidene-Ruthenium-Tin Catalysts for the Formation of Fatty Nitriles 2 and Esters via Cross-Metathesis of Plant Oil Derivatives

Xiaowei Miao (1) , A. Blokhin (2) , A. Pasynskii (2) , S. Nefedov (2) , S. N. Osipov (3) , Thierry Roisnel (1) , Christian Bruneau (1) , Pierre H. Dixneuf (1)

1 ISCR - Institut des Sciences Chimiques de Rennes
2 IGIC - N. S. Kurnakov Institute of General and Inorganic Chemistry
3 INEOS - A. N. Nesmeyanov Institute of Organoelement Compounds

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.

Domaines: Catalyse

Xiaowei Miao, A. Blokhin, A. Pasynskii, S. Nefedov, S. N. Osipov, et al.. Alkylidene-Ruthenium-Tin Catalysts for the Formation of Fatty Nitriles 2 and Esters via Cross-Metathesis of Plant Oil Derivatives. Organometallics, 2010, 29, pp.5257-5262. ⟨10.1021/om100372b⟩. ⟨hal-00564245⟩