Combined Ab Initio Computational and Infrared Spectroscopic Study of the cis- and trans-Bis(glycinato)copper(II) Complexes in Aqueous Environment

Abstract

The cis- and trans-bis(glycinato)copper(II) complexes in aqueous solution have been investigated by means of a combined theoretical and experimental approach. The conducted quantum mechanical charge field molecular dynamics (QMCF-MD) studies, being the first quantum mechanical simulations of organometallic complexes by this method, yielded accurate structural details of the investigated isomers as well as novel dynamic data, which has successfully been confirmed and extended by subsequent mid-infrared measurements. The spectroscopic results, critically assessed by adjacent multivariate data analysis, indicate an isomeric stability at ambient conditions, vanishing at elevated temperatures.

The hydration properties of Gd(III) and Tb(III): An ab initio quantum mechanical molecular dynamics study

“…In this study the ab initio quantum mechanical charge-field molecular dynamics (QMCF-MD) approach [2,3] has been used as it had already yielded accurate insight into the hydration properties of a wide range of cations [4][5][6] and anions [7], as well as complexes [8][9][10]. In particular, a number of trivalent cations of the lanthanoide [11][12][13][14][15] and actinoide series [16] have already been successfully investigated, the results being in very good agreement with experimental data where available.…”

A Comparative Study of [CaEDTA]2– and [MgEDTA]2–: Structural and Dynamical Insights from Quantum Mechanical Charge Field Molecular Dynamics

“…In this work an extended QM/MM technique, known as QMCF, [40][41][42][43] is used which has proven to yield excellent results for the investigation of coordination complexes. [45][46][47][48][49] For more information on the methodology the reader is referred to the respective original literature. [40][41][42][43] A crucial step for QM calculations is the assignment of suitable basis sets for the chemical species in the QM region, i.e.…”

“…HF on the other hand lacks of a proper description of electron correlation, but when double-ζ basis sets + polarisation functions are applied excellent results are obtained. [45][46][47][48][49]55 Thus, HF was chosen as compromise between accuracy of results and computational cost. For both MD simulations of [CaEDTA] 2− and [MgEDTA] 2− in aqueous solution a cubic periodic water box containing 2500 explicitly treated water molecules was used.…”

Conformational Analyses of Physiological Binary and Ternary Copper(II) Complexes with l‐Asparagine and l‐Histidine; Study of Tridentate Binding of Copper(II) in Aqueous Solution

“…[44,45] Specifically, ΔV between the lowest-energy tNONO and cNONO conformers dropped from 35.0 kJ mol À 1 (ΔV vacuum ) to 4.4 kJ mol À 1 (ΔV water ). This seems to be a common characteristic for trans and cis glycinato-mode Cu(aa) 2 conformers, that they have similar stability in aqueous solution at room temperature [18,19,[57][58][59][60][61] while the trans conformers are more stable as isolated compounds. [17][18][19][58][59][60][61][62][63] Comparison of relative electronic energies (ΔV) for the lowest-energy conformers in each of the in-plane modes in the gas phase and PCM-estimated aqueous solution ( Figure 5) shows that ΔV are much lower by PCM than in the gas phase (Table S39).…”