209330-50-7Relevant academic research and scientific papers
Preparation of hydrido(vinylidene)ruthenium(II) complexes and a one-pot synthesis of Grubbs-type ruthenium carbenes
Stueer, Wolfram,Weberndoerfer, Birgit,Wolf, Justin,Werner, Helmut
, p. 1796 - 1803 (2005)
Treatment of the hydrido(dihydrogen) compound [RuHCl(H2) (PCy3)2] 1 with alkynes RC≡CH (R = H, Ph) afforded the hydrido(vinylidene) complexes [RuHCl(=C=CHR)(PCy3)2] 2, 3 which react with HCl or [HPCy3]Cl to give the corresponding Grubbs-type ruthenium carbenes [RuCl2(=CHCH2R)(PCy 3)2] 4, 5. The reaction of 2 (R = H) with DCl, or D 2O in the presence of chloride sources, led to the formation of [RuCl2(=CHCH2D)(PCy3)2] 4-d 1. Based on these observations, a one-pot synthesis of compounds 4 and 5 was developed using RuCl3·3H2O as the starting material. The hydrido(vinylidene) derivative 2 reacted with CF 3CO2H and HCN at low temperatures to yield the carbene complexes [RuCl(X)(=CHCH3)(PCy3)2] 6,7, of which 7 (X = CN) was characterized crystallographically. Salt metathesis of 2 with CF3CO2K and KI led to the formation of [RuH(X)(=C=CH2)(PCy3)2] 8, 9. The bis(trifluoracetato) and the diiodo compounds [RuX2(=CHCH 3)(PCy3)2] 10,11 as well as the new phosphine P(thp)3 12 (thp = 4-tetrahydropyranyl) and the corresponding complex [RuCl2(=CHCH3){P(thp)3}2] 14 were also prepared. The catalytic activity of the ruthenium carbenes 4-7, 10, 11 and 14 in the olefin cross-metathesis of cyclopentene and allyl alcohol was investigated. The Royal Society of Chemistry 2005.
