Untitled

DFT B3LYP Quantum-Chemical Calculation of Molecular Structures of (6.6.6)-Macrotricyclic MII Comp-lexes with (N,N,N,N)-Coordinating Ligand Formed in the MII– Hydrazinomethanethiohydrazide– Propanone Triple Systems

“…The 6-31G(d) basis, set where each inner atom orbital (AO) is described by six functions of Gaussian type (GTO), valence 2s AO-by three GTO, valence р-АО -by one GTO, with addition of polarization d-GTO to each р-function, was used. Conformity of the found stationary points to energy minima in all cases was proved by calculation of the second derivatives of energy on (1) Macrotricyclic M II Complexes with (N,N,N,N)-Coordinating Ligand co-ordinates of atoms. Each equilibrium structure corresponding to points of a minimum on surfaces of potential energy, had only material values of frequencies.…”

“…Previously we have reported [1][2][3] on the template syntheses in the M II ion-hydrazinomethanethiohydrazide [H 2 N-NH-C(=S)-NH-NH 2 ]-propanone H 3 C-C(=O)-CH 3 triple systems proceeding into metalhexacyanoferrate(II) gelatin-immobilized matrix implants (MHF-GIM, M = Co, Ni, Cu). Some details concerning the coordination of ligands formed as a result of such syntheses (what is known as chelating agent), to the corresponding metal ion were also established.…”

“…According to mass-spectroscopy data, among other products of such synthesis, (6.6.6)macro-tricyclic metalcomplexes (I) with 4,6,6-trimethyl-2,3,7,8-tetraazanonen-3-dithiohydrazide-1,9, are present in small amounts. Such metalmacrocyclic species are formed in the corresponding GIM according to the probable general reaction (1) The three-dimensional structure of metalmacrocyclic compounds (I) is an open question up to now because attempts to obtain their crystals suitable for X-ray diffraction analysis, from gelatin matrix, were unsuccesful. In this connection, it appears expedient to carry out calculation of geometrical parameters of metalcomplexes formed in the systems under examination, using any of the modern quantum-chemical methods able to provide independent objective data about their parameters.…”

Complexing processes in M(II)-dithiomalonamide-diacetyl triple systems (M= Ni, Cu) in ethanol solution and in a metal(II)hexacyanoferrate(II) gelatin-immobilized matrix materials

“…All the other experimental techniques were as reported in our earlier work [1][2][3][4][5][6]. As previously the kinetics of complexing processes designed by the D Ñ ¼ f(C F , C L 0 , t) relationships {D Ñ is the absorbance of the metal chelate GIM, corresponding to an initial concentration of M 2 [Fe(CN) 6 ] (M ¼ Ni, Cu) in a GIM (C F , mol dm )3 )}, the concentration of the corresponding ligand synthon in solution in contact with this GIM (C L 0 , mol dm )3 ) and the complexing process time (t, min) are given.…”

Quantum-Сhemical Сalculations of (5.6.5)Macrotricyclic Complexes in Some MII – (N,S)-Ambidentate Ligson – (O)-Ligson Triple Systems

“…This synthesis may be facilitated by using biopolymer-immobilized matrix systems providing preliminary decrease of entropy of reactionary medium. [6][7][8] One of the ligsons in given process (L1) may be organic compound containing two (C=S) groups and N donor atoms, for example ethanedithioamide-1,2, H 2 N-C(=S)-C(=S)-NH 2 , or propanedithioamide-1,3, H 2 N-C(=S)-CH 2 -C(=S)-NH 2 . As another ligson (L2), some organic compounds containing one or two carbonyl groups (C=O), may be used, for example methanal H 2 C=O, propanone H 3 C-C(=O)-CH 3 , ethanedial-1,2 HC(=O)-CH(=O), etc.…”