Collect. Czech. Chem. Commun. 2005, 70, 313-326

Conformational Influence on Deprotonation of Bis(methoxycarbimido)amine Ligand

Kateřina Brudíkováa, Martin Brezab,* and Pavel Májekc

a Department of Physical and Applied Chemistry, Brno University of Technology, CZ-612 00 Brno, Czech Republic
b Department of Physical Chemistry, Slovak Technical University, SK-81237 Bratislava, Slovakia
c Department of Analytical Chemistry, Slovak Technical University, SK-81237 Bratislava, Slovakia


Using MP2 treatment, the optimal geometries and corresponding electronic structures of [HN=C(OCH3)-N-C(OCH3)=NH]- (mici-), HN=C(OCH3)-NH-C(OCH3)=NH (Hmici), [Cu(mici)]2 and [Cu(Hmici)2]2+ were investigated. In agreement with experimental data, the preferred conformation of our systems depends on the ligand: mici- prefers the methoxy groups oriented to the central N atom whereas Hmici prefers the opposite orientations. The shielding by the methoxy groups is the main reason for the preferred site of deprotonation. The deprotonation of the [Cu(Hmici)2]2+ complex is more probable than that of the free Hmici ligand. Due to preferred conformation of this complex, the deprotonation proceeds by cleavage of the central N-H bond.

Keywords: MP2 geometry optimization; Copper complexes; Bis(methoxycarbimido)amine; Topological analysis of electron density; Ab initio calculations; N-Ligands; Imidates.

References: 21 live references.