Effect of CO substitution on the redox properties of Fischer Mo(0) carbene complexes Mo(CO)5=C(Y)(2-Furyl), Y = OEt, NHCy or NH2. (20th August 2015)

• Record Type: Journal Article
• Authors: Landman, Marilé; Levell, Tamzyn J.; Buitendach, Blenerhassitt E.; Conradie, Marrigje M.; Conradie, Jeanet
• Is Part Of: Electrochimica acta. Volume 174(2015)
• Page Start: 282
• Page End: 289
• Publication Date: 2015-08-20
• Subjects: Fischer carbene -- Molybdenum -- Electrochemistry -- DFT -- Cyclic voltammetry; Electrochemistry -- Periodicals; Electrochemistry, Industrial -- Periodicals; 541.37
• DOI: 10.1016/j.electacta.2015.05.191
• Languages: English
• ISSNs: 0013-4686

Abstract

Graphical abstract: Highlights: Oxidation potential (CO)5 Mo-carbene > (CO)4 (PPh3 )Mo-carbene > (CO)3 (dppe)Mo-carbene Different oxidation potential for fac and mer isomers Different oxidation potential for cis and trans isomers Lower oxidation potential for amino- than ethoxy carbenes Abstract: An electrochemical study, complimented by a density functional theory study, on nine Mo(0) Fischer carbene complexes of the formula [(CO)3 (L, L′)Mo=C(Y)(2-furyl)] with Y = OEt, NH2 or NHCy; L, L′ = CO, CO; PPh3, CO or dppe (diphenyl phosphinoethane), showed that the Mo-based oxidation process can be systematically tuned by the substitution of the CO groups: (most difficult to oxidize, largest oxidation potential E pa ) [(CO)5 Mo-carbene complex] > [(CO)4 (PPh3 )Mo-carbene complex] > [(CO)3 (dppe)Mo-carbene complex]. The one-electron reduction of the complexes that is mainly localized on the carbene carbon, followed the same trend.