8 research outputs found
26th Annual Computational Neuroscience Meeting (CNS*2017): Part 3 - Meeting Abstracts - Antwerp, Belgium. 15–20 July 2017
This work was produced as part of the activities of FAPESP Research,\ud
Disseminations and Innovation Center for Neuromathematics (grant\ud
2013/07699-0, S. Paulo Research Foundation). NLK is supported by a\ud
FAPESP postdoctoral fellowship (grant 2016/03855-5). ACR is partially\ud
supported by a CNPq fellowship (grant 306251/2014-0)
Synthesis, Structure, and Electrochemistry of Fischer Alkoxy- and Aminocarbene Complexes of Tungsten: The Use of DFT To Predict and Understand Oxidation and Reduction Potentials
Reactions 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.Norwegian Supercomputing Program (NOTUR) through a grant of computer
time (Grant No. NN4654K) (J.C.), the South African National Research Foundation (J.C.) and the Central Research Fund of the University of the Free State, Bloemfontein (J.C.), and the University of Pretoria (M.L. and P.H.v.R.).http://pubs.acs.org/journal/orgnd7hb201