138367-77-8Relevant academic research and scientific papers
Metathesis catalysts in confining reaction fields - Confinement effects vs. surface effects
Polarz, Sebastian,Voelker,Jeremias, Felix
, p. 577 - 584 (2010)
It has been recognized previously that inside nanosized cavities like in mesoporous materials a small ensemble situation can be realized. The limited number of reactants per confinement leads to unusual chemical behaviour whenever inter- vs. intramolecular pathways compete against each other. Therefore, the metathesis reaction might represent a chemical process for which the product distribution is influenced by a confining reaction field. In the current paper we report about the unusual reactivity of the Grubbs generation I catalyst inside mesoporous silica materials. It has been observed that due to a combination of confinement and surface effects the Grubbs catalyst is not stable inside small pores. It quickly rearranges to a variety of unexpected products. However, the undesired deactivation of the catalyst can be prohibited by surface modification of the silica surfaces. The Royal Society of Chemistry.
Synthesis and ligand substitution reactions of κ4-B,S,S′,S′′-ruthenaboratranes
Foreman, Mark R. St.-J.,Hill, Anthony F.,Ma, Chenxi,Tshabang, Never,White, Andrew J. P.
, p. 209 - 219 (2019)
A range of ruthenaboratranes of the form [Ru(CO)L{κ4-B,S,S′,S′′-B(mt)3}] (mt = N-methylmercaptoimidazolyl) have been prepared either by substitution of the PPh3 ligand in [Ru(CO)(PPh3){κ4-B,S,S′,S′′-B(mt)3}] by L (L = PMe2Ph, PMe3, P(OMe)3, P(OEt)3, P(OPh)3) or reactions of [RuCl(R)(CO)Ln] (R = Ph, CH═CHPh; n = 2, L = PCy3; n = 3, L = P(OMe)3, PMe2Ph) with Na[HB(mt)3].
Degradation of the first-generation Grubbs metathesis catalyst with primary alcohols, water, and oxygen. Formation and catalytic activity of ruthenium(II) monocarbonyl species
Dinger, Maarten B.,Mol, Johannes C.
, p. 1089 - 1095 (2003)
The first-generation Grubbs metathesis catalyst (PCy3)22Ru(=CHPh)(Cl)2 (1) was reacted with primary alcohols at 70 °C to give the monohydride species (PCy3)2(CO)Ru(Cl)(H) (4) in ～20% yield. Addition of either an inorganic or organic base greatly facilitated the formation of the hydride, and 4 could be isolated in >70% yield in the case of 1-propanol and triethylamine. Analysis of the reaction products and labeling experiments revealed that 4 was formed via a noncatalytic alcohol dehydrogenation pathway. When benzyl alcohol was used, (PCy3)2(CO)Ru(Cl)(Ph) (5) was formed, this also being one of the products of the decomposition of 1 by oxygen in both solid and solution states. Complexes 4 and 5 were found to be active and selective alkene double-bond isomerization catalysts.
