OCTAHEDRAL METAL CARBONYLS. 56.1KINETICS AND MECHANISM OF LIGAND EXCHANGE IN [4-METHYL,1,2-BIS(METHYLTHIO)BENZENE]-TETRACARBONYLCHROMIUM(O)

Autor:	Canan S. Binzet, Jose E. Cortes, Gerard R. Dobson
Rok vydání:	1986
Předmět:	Reaction mechanism Ligand Stereochemistry Kinetics Metal carbonyl Medicinal chemistry chemistry.chemical_compound chemistry Nucleophile Chlorobenzene Materials Chemistry Physical and Theoretical Chemistry Benzene Isopropyl
Zdroj:	Journal of Coordination Chemistry. 14:215-222
ISSN:	1029-0389 0095-8972
Popis:	The kinetics and mechanism of displacement of the chelating ligand bmtb (= 4-methyl-1,2-bis(methylthio)benzene) from (bmtb)Cr(CO)4 by L (= tri(isopropyl) phosphite, triethyl phosphite) in chlorobenzene (CB) and 1,2-dichloroethane (DCE) have been studied. The reaction obeys a rate law, -d[(bmtb)Cr(CO)4]/dt = k[(bmtb)Cr(CO)4][L]. Although two limiting mechanisms, one involving rate-determining nucleophilic attack at the metal atom and the other rate-determining reversible ring-opening may be envisioned, activation data in CB taken over a 75 degree temperature range and a thousand-fold change in k demonstrate that only one reaction pathway is accessible. Despite the slightly negative entropies of activation observed, the latter mechanism is favoured based upon a comparison of the data to that obtained for other closely-related systems.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::90545868f5db7610ae98b5bdd62fd9bc https://doi.org/10.1080/00958978608073910 Zobrazit plný text záznamu