Kinetics and mechanism of ligand substitution reactions in [cis-M(CO)4(amine)(EPh3)] complexes (M = Mo, W; amine = pyridine, piperidine; E = As, Sb). Issue 22 (17th November 2017)

• Record Type: Journal Article
• Authors: Asali, Khalil J.; El-khateeb, Mohammad; Foudeh, Yousef; Abul-Futouh, Hassan
• Is Part Of: Journal of coordination chemistry. Volume 70:Issue 22(2017)
• Page Start: 3810
• Page End: 3822
• Publication Date: 2017-11-17
• Subjects: Group 6 metals -- carbonyl -- substitution -- kinetics -- mechanism; Coordination compounds -- Periodicals; 541.2242
• DOI: 10.1080/00958972.2017.1402117
• Languages: English
• ISSNs: 0095-8972

Abstract

Abstract: Group 6 metal carbonyls [ cis -M(CO)4 (amine)(EPh3 )] (M = Mo, W; amine = piperidine (pip), pyridine (py); E = As, Sb) have been prepared and characterized. These complexes react thermally in chlorobenzene solutions with phosphine or phosphite ligands (= L) to give cis - and trans -M(CO)4 (L)(EPh3 ) products. Kinetics of amine substitution by L in these complexes, under pseudo -first-order conditions, indicate that these reactions proceed by a rate law that is first-order in concentration of the metal complex. Rate constants and activation parameters for these reactions have been determined and are discussed. Competition studies for the [M(CO)4 (EPh3 )] intermediates show that these intermediates are highly reactive and react almost indiscriminately with various incoming nucleophiles with slight preference for more basic ones. Abstract :