Back to basics: identification of reaction intermediates in the mechanism of a classic ligand substitution reaction on Vaska's complex. Issue 4 (4th January 2016)

• Record Type: Journal Article
• Authors: Durango-García, Clara J.; Jalife, Said; Cabellos, José Luis; Martínez, Saul H.; Jimenez-Halla, J. Oscar C.; Pan, Sudip; Merino, Gabriel; Montiel-Palma, Virginia
• Is Part Of: RSC advances. Volume 6:Issue 4(2016)
• Page Start: 3386
• Page End: 3392
• Publication Date: 2016-01-04
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c5ra20969b
• Languages: English
• ISSNs: 2046-2069

Abstract

Abstract : The mechanism of methylation of Vaska's complex trans -[ClIr(CO)(PPh3 )2 ] by trimethylgallium was studied and the identification of the spectroscopically detected intermediates was achieved with the aid of computational methods. Abstract : The mechanism of methylation of Vaska's complex trans -[ClIr(CO)(PPh3 )2 ] by trimethylgallium was studied and the identification of the spectroscopically detected intermediates was achieved with the aid of computational methods. The reaction pathway, computed by means of density functional theory (M05-2X-D3/def2-SVP), involves the initial formation of a chloride-bridged adduct trans -[(Cl·GaMe3 )Ir(CO)(PPh3 )2 ] to then proceeds to a transition state [(μ2 -Cl, C-ClMeGaMe2 )Ir(CO)(PPh3 )2 ]. This transition state subsequently evolves to the methylated adduct [MeIr(CO)(PPh3 )2 ·(GaMe2 Cl)] to finally release the alkylated product trans -[MeIr(CO)(PPh3 )2 ] together with GaMe2 Cl.