Landman, MarilePretorius, RenéBuitendach, Blenerhassitt E.Van Rooyen, Petrus H.Conradie, Jeanet2014-05-122014-10-312013-10Landman, M, Pretorius, R, Buitendach, BE, Van Rooyen, PH & Conradie, J 2013, 'Synthesis, structure and electrochemistry of Fischer alkoxy- and aminocarbene complexes of tungsten : the use of DFT to predict and understand oxidation and reduction potentials', Organometallics, vol. 32, no. 19, pp. 5491-5503.0276-7333 (print)1520-6041 (online)10.1021/om400778zhttp://hdl.handle.net/2263/39770Reactions of Fischer alkoxycarbene complexes [W(CO)5{C(OEt)Ar}], Ar = thienyl (1) or furyl (2), with ethylene diamine lead to the formation of two different reaction products: an aminolysis product (5 or 6) where the ethoxy substituent of the carbene ligand is replaced by the ethylene diamine moiety, as well as a chelated product where aminolysis and substitution of one carbonyl ligand had taken place, yielding 7 or 8. Aminolysis of 1 and 2 with cyclohexyl amine (CHA) produced the aminocarbene complexes 3 (Ar = thienyl) and 4 (Ar = furyl). Complexes 1-8 are electrochemically investigated by means of cyclic voltammetry. The relative shifts in the oxidation and reduction potentials are discussed and related to density functional theory (DFT) calculated energies. DFT calculations further show that the oxidation center is located on the metal and the carbonyl groups, while the reduction center is localized on the carbene moiety and is strongly influenced by the electronic properties of its substituents. Crystal structures of 1-4, 6 and 8 are reported.en© 2013 American Chemical Society.This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, after peer review and technical editing by the publisher. To access the final edited and published work see : Organometallics, vol. 32, no. 19, pp. 5491-5503, 2013,. doi : 10.1021/om400778z Organometallics is available online at : http://pubs.acs.org/journal/orgnd7SynthesisStructureElectrochemistry of Fischer alkoxyAminocarbene complexes of TungstenPostprint Article