Correlation of electrochemistry, nucleophilicity and density functional calculations of the cis-dithiolate (bme*-daco)Ni Academic Article

abstract

• Upon the sequential stoichiometric addition of methyl iodide to acetonitrile solutions of the square planar nickel (II) complex of N,N'-bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctane, (bme(*)-daco)Ni, mono- and bis-methylated thioether compounds were isolated. Both are crystallographically and electrochemically characterized and compared to analogues of N,N'-bis(2-mercaptoethyl)-1,5-diazacyclooctane, (bme-daco)Ni. Density functional theory calculations carried out at the B3LYP level using the LANL2DZ basis set with modified exponents compared HOMO/LUMO energies for the dithiolates, the mono-S-methylated and bis-S-methylated complexes. The presence of the methyl groups on the -carbon next to the sulfur creates steric encumbrance about the thiolate sulfurs, but there was found no significant differences in the frontier molecular orbitals. The more positive shifts of the Ni(II/I) reduction potentials are reflected by changes in LUMO energies upon S-methylation. (C) 2000 Elsevier Science S.A.

authors

• Darensbourg, Marcetta

published proceedings

• INORGANICA CHIMICA ACTA

author list (cited authors)

• Bellefeuille, J. A., Grapperhaus, C. A., Derecskei-Kovacs, A., Reibenspies, J. H., & Darensbourg, M. Y.

citation count

• 19

complete list of authors

• Bellefeuille, JA||Grapperhaus, CA||Derecskei-Kovacs, A||Reibenspies, JH||Darensbourg, MY

publication date

• April 2000

publisher

• Elsevier  Publisher

published in

• Inorganica Chimica Acta  Journal

keywords

• Density Functional Calculations
• Dithiolate Complexes
• Electrochemistry
• Nickel(ii) Complexes
• Nucleophilicity

Digital Object Identifier (DOI)

• 10.1016/S0020-1693(99)00575-7

start page

• 73

end page

• 81

volume

• 300

URL

• http%3A%2F%2Fdx.doi.org%2F10.1016%2Fs0020-1693%2899%2900575-7