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Abstract:

Quantum chemical calculations using density functional theory have been carried out to investigate the influence of aqueous solvation on the structure and bonding in [Fe(CN) 5 L] 3- with L an aliphatic amine (ammonia, methylamine, hydrazine, and ethylenediamine). Gas phase equilibrium geometries were fully optimized at the generalized gradient approximation (GGA) level. Solvent effects were modeled within the DFT methodology by using a discrete electrostatic representation of the water molecules in the first solvation shell. For the hydrazine and ethylenediamine complexes in vacuum we found two internal hydrogen bonds between the terminal amino group hydrogens and two equatorial cyanide ligands. However, considering the first solvation shell, an open structure in which the terminal amino group is solvated by water molecules becomes more stable in the ethylenediamine case. Metal-L dissociation energies were computed in vacuum, taking the first solvation shell into account. The results obtained were compared with experimental kinetic data in aqueous solution in order to assess the role of solvation in the reactivity of these complexes.

Registro:

Documento: Artículo
Título:Structure, solvation, and bonding in pentacyano(L) ferrate (II) ions (L=aliphatic amine): A density functional study
Autor:Gonz ález-Lebrero, M.C.; Turjanski, A.G.; Olabe, J.A.; Estrin, D.A.
Filiación:Departamento de Quimica Inorganica, Analitica y Quimica Fisica/INQUIMAE, Universidad de Buenos Aires, Pabellón 2, Buenos Aires, Argentina
Palabras clave:DFT; Solvent effects; Transition metal complexes; aliphatic amine; ammonia; ethylenediamine; ferric ferrocyanide; hydrazine; methylamine; aqueous solution; article; calculation; chemical binding; chemical reaction; chemical structure; controlled study; density; electricity; hydrogen bond; mathematical computing; methodology; priority journal; quantum chemistry; solvation; vacuum
Año:2001
Volumen:7
Número:7
Página de inicio:201
Página de fin:206
DOI: http://dx.doi.org/10.1007/S008940100035
Título revista:Journal of Molecular Modeling
Título revista abreviado:J. Mol. Model.
ISSN:16102940
CODEN:JMMOF
CAS:ammonia, 14798-03-9, 51847-23-5, 7664-41-7; ethylenediamine, 107-15-3; ferric ferrocyanide, 12240-15-2, 14038-43-8, 14433-93-3, 14460-02-7; hydrazine, 10217-52-4, 13775-80-9, 18500-32-8, 302-01-2, 7803-57-8; methylamine, 74-89-5
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_16102940_v7_n7_p201_GonzalezLebrero

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Citas:

---------- APA ----------
Gonz ález-Lebrero, M.C., Turjanski, A.G., Olabe, J.A. & Estrin, D.A. (2001) . Structure, solvation, and bonding in pentacyano(L) ferrate (II) ions (L=aliphatic amine): A density functional study. Journal of Molecular Modeling, 7(7), 201-206.
http://dx.doi.org/10.1007/S008940100035
---------- CHICAGO ----------
Gonz ález-Lebrero, M.C., Turjanski, A.G., Olabe, J.A., Estrin, D.A. "Structure, solvation, and bonding in pentacyano(L) ferrate (II) ions (L=aliphatic amine): A density functional study" . Journal of Molecular Modeling 7, no. 7 (2001) : 201-206.
http://dx.doi.org/10.1007/S008940100035
---------- MLA ----------
Gonz ález-Lebrero, M.C., Turjanski, A.G., Olabe, J.A., Estrin, D.A. "Structure, solvation, and bonding in pentacyano(L) ferrate (II) ions (L=aliphatic amine): A density functional study" . Journal of Molecular Modeling, vol. 7, no. 7, 2001, pp. 201-206.
http://dx.doi.org/10.1007/S008940100035
---------- VANCOUVER ----------
Gonz ález-Lebrero, M.C., Turjanski, A.G., Olabe, J.A., Estrin, D.A. Structure, solvation, and bonding in pentacyano(L) ferrate (II) ions (L=aliphatic amine): A density functional study. J. Mol. Model. 2001;7(7):201-206.
http://dx.doi.org/10.1007/S008940100035