title: Experimental and theoretical charge density distribution in two ternary cobalt(III) complexes of aromatic amino acids.
abstract: The experimental charge density distributions in two optically active isomers of a Co complex have been determined. The complexes are Delta-alpha-[Co(R,R-picchxn)(R-trp)](ClO4)2.H2O) (1) and Lambda-beta1-[Co(R,R-picchxn)(R-trp)](CF3SO3)2) (2), where picchxn is N,N'-bis(2-picolyl-1,2-diaminocyclohexane) and R-trp is the R-tryptophane anion. The molecular geometries of 1 and 2 are distinguished by the presence in complex 1 of intramolecular pi...pi stacking interactions and the presence in complex 2 of intramolecular hydrogen bonding. This pair of isomers therefore serves as an excellent model for studying noncovalent interactions and their effects on structure and electron density and the transferability of electron density properties between closely related molecules. For complex 2, a combination of X-ray and neutron diffraction data created the basis for a X-N charge density refinement. A topological analysis of the resulting density distribution using the atoms in molecules methodology is presented along with d-orbital populations, showing that the metal-ligand bonds are relatively unaltered by the geometry changes between 1 and 2. The experimental density has been supplemented by quantum chemical calculations on the cobalt complex cations: close agreement between theory and experiment is found in all cases. The energetics of the weak interactions are analyzed using both theory and experiment showing excellent quantitative agreement. In particular it is found that both methods correctly predict the stability of 2 over 1. The transferability between isomers of the charge density and derived parameters is investigated and found to be invalid for these structurally related systems.
authors: Department of Chemistry, Aarhus University, Langelandsgade 140, DK-8000 Aarhus C, Denmark.
authors: Jacob
authors: J
authors: Overgaard
authors: Mark P
authors: MP
authors: Waller
authors: Ross
authors: R
authors: Piltz
authors: James A
authors: JA
authors: Platts
authors: Paul
authors: P
authors: Emseis
authors: Peter
authors: P
authors: Leverett
authors: Peter A
authors: PA
authors: Williams
authors: David E
authors: DE
authors: Hibbs
mesh_terms: D024322:Amino Acids, Aromatic / Q000737:chemistry*; D000838:Anions; D001703:Biophysics / Q000379:methods; D002412:Cations; D002627:Chemistry, Physical / Q000379:methods; D003035:Cobalt / Q000737:chemistry*; D018360:Crystallography, X-Ray / Q000379:methods; D004123:Dimethylamines / Q000737:chemistry; D004583:Electrons; D006860:Hydrogen Bonding; D008962:Models, Theoretical; D008968:Molecular Conformation; D009502:Neutrons; D020033:Protein Isoforms; D011758:Pyrroles / Q000737:chemistry; D011789:Quantum Theory; D012984:Software; D013052:Spectrometry, X-Ray Emission / Q000379:methods; D014364:Tryptophan / Q000737:chemistry; D014961:X-Ray Diffraction
chemical_list: D024322:Amino Acids, Aromatic; D000838:Anions; D002412:Cations; D004123:Dimethylamines; D020033:Protein Isoforms; D011758:Pyrroles; D003035:Cobalt; D014364:Tryptophan