Geometrical Structures of the First Solvation Shell of the[PdCl4]~(2-)Core: Charge-Dipole vs Dipole-Dipole Interaction of(Pd~(II)…Solvent)

摘要

Since the weak vertical interactions of(Pt…H2O)in square planar Pt complexes were theoretically suggested by Kozelka et al.,axial metal-solvent interactions in square planar d~8-metal complexes have been the focus of various theoretical and experimental approaches focused on both geometrical structure and catalytic activity on reactions.The weak(M…L)interaction for the solvation is formed from the various interactive components like the charge-dipole,dipole-dipole,and hydrogen bond interactions.From the results of Kozelka et al.,the square pyramidal structures of Pt complexes with vertical(Pt…HO,Pt…OH)interactions are optimized.The binding energies of(OH…Pt)and(HO …Pt)are about 11 and 4 kcal/mol,respectively.The distance of the apical(Pt…O)interaction is about 3.3-3.5 A.From the calculations of the Deeth group,we know the square pyramidal structures with vertical(M…OH2)interactions,as optimized at the LDA level.The binding energy of(M… OH2)is about 5 kJ/mol,and the(M…OH2)distance is about 2.6-2.8 A.The five-coordinate structure of the GC calculation was not optimized.