Geometry and electronic structure of bis-(glycinato)-CuII•2H2O complexes as studied by density functional B3LYP computations

被引:44
作者
de Bruin, TJM [1 ]
Marcelis, ATM [1 ]
Zuilhof, H [1 ]
Sudhölter, EJR [1 ]
机构
[1] Wageningen Univ, Organ Chem Lab, NL-6703 HB Wageningen, Netherlands
关键词
D O I
10.1039/a903018b
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Geometry optimizations using the density functional method B3LYP with a variety of basis sets were performed on bis-(glycinato)-(CuBO)-B-II . 2H(2)O complexes. The geometry and electronic structure were probed with various basis sets and natural population analysis. Geometry optimizations should at least be performed with the all-electron basis set 6-311+G(d,p) or with C, H, N, O=6-311+G(d,p) and an effective core potential for Cu; spurious minima were found with smaller basis sets. Two real minima were found on these potential energy surfaces: a trans configurated complex of C-i symmetry, and a cis configurated complex with C-1 symmetry. In vacuo the trans structure is more stable by 18 kcal mol(-1), which reduces to 10 kcal mol(-1) in a dielectric medium representing water. The final geometries strongly depend on the number of hydrogen bonds formed between the coordinating water molecules and the amino and carboxylate functionalities, as formation of such hydrogen bonds competes with axial Cu-II... OH2 interactions.
引用
收藏
页码:4157 / 4163
页数:7
相关论文
共 53 条
[1]  
ALLENMARK S, 1991, CHROMATOGRAPHIC ENAN, P144
[2]  
ANGELO PD, 1998, INORG CHEM, V102, P3114
[3]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[4]   MOLECULAR MECHANICS CALCULATIONS OF TRANSITION-METAL COMPLEXES [J].
BERNHARDT, PV ;
COMBA, P .
INORGANIC CHEMISTRY, 1992, 31 (12) :2638-2644
[5]   Theoretical study of the 15- and 17-electron structures of cyclopentadienylchromium(III) and cyclopentadienylmolybdenum(III) complexes. Dichloride and dimethyl compounds [J].
Cacelli, I ;
Keogh, DW ;
Poli, R ;
Rizzo, A .
JOURNAL OF PHYSICAL CHEMISTRY A, 1997, 101 (50) :9801-9812
[6]   THE RELATION BETWEEN LIGAND STRUCTURES, COORDINATION STEREOCHEMISTRY, AND ELECTRONIC AND THERMODYNAMIC PROPERTIES [J].
COMBA, P .
COORDINATION CHEMISTRY REVIEWS, 1993, 123 (1-2) :1-48
[7]  
Comba P., 1995, MOL MODELING INORGAN
[8]   CHIRAL RECOGNITION AND SEPARATION OF AMINO-ACIDS BY MEANS OF A COPPER(II) COMPLEX OF HISTAMINE MONOFUNCTIONALIZED BETA-CYCLODEXTRIN [J].
CORRADINI, R ;
DOSSENA, A ;
IMPELLIZZERI, G ;
MACCARRONE, G ;
MARCHELLI, R ;
RIZZARELLI, E ;
SARTOR, G ;
VECCHIO, G .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (22) :10267-10274
[9]   SEPARATION OF AMINO-ACID ENANTIOMERS USING MICELLAR-ENHANCED ULTRAFILTRATION [J].
CREAGH, AL ;
HASENACK, BBE ;
VANDERPADT, A ;
SUDHOLTER, EJR ;
VANTRIET, K .
BIOTECHNOLOGY AND BIOENGINEERING, 1994, 44 (06) :690-698
[10]  
DAVANKOV VA, 1983, ADV CHROMATOGR, V22, P71