Molecular Modeling of Ruthenium Alkylidene Mediated Olefin Metathesis Reactions. DFT Study of Reaction Pathways

Autor:	Serguei Fomine, Sergio Martinez Vargas, Mikhail A. Tlenkopatchev
Rok vydání:	2002
Předmět:	Molecular model Olefin metathesis Chemistry Stereochemistry Organic Chemistry chemistry.chemical_element Medicinal chemistry Ruthenium Inorganic Chemistry chemistry.chemical_compound Salt metathesis reaction Dissociative substitution Physical and Theoretical Chemistry Phosphine
Zdroj:	Organometallics. 22:93-99
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om020581w
Popis:	Three possible reaction pathways have been studied for the Cl2(PMe3)2RuCH2 and Cl2(PCy3)2RuCH2 (Cy = cyclohexyl) mediated metathesis reaction of propylene by quantum-mechanical DFT calculations. It was found that in all cases the metathesis reaction proceeds via dissociative substitution of a phosphine ligand with propylene, giving a monophosphine complex. This tendency increases with ligand volume, and in the case of smaller PMe3 groups it is the entropy contribution to the reaction energetics that causes the monophosphine complex to participate in the metathesis reaction, according to the modeling data.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::9d1153703a6ce09a88fb0894631bbe3f https://doi.org/10.1021/om020581w Zobrazit plný text záznamu