Solvent effects on the relative stability of the PdCl2(H2O)n and PdHCl(H2O)n cis and trans isomers
- 1 September 1996
- journal article
- research article
- Published by Taylor & Francis in Molecular Physics
- Vol. 89 (1) , 279-296
- https://doi.org/10.1080/002689796174137
Abstract
The relative stability of the cis and trans isomers of the PdCl2(H2O)n and PdHCl(H2O)n complexes with up to six water ligands has been studied. Optimized geometries are discussed with particular emphasis on the positions taken by the second sphere water ligands. It is found that the empty coordination site above palladium is not as attractive for the second sphere ligands as might have been anticipated. Two types of hydrogen bonds, of O-H...Pd and O-H...H-Pd were found, which have only recently been detected experimentally. The effect of a water solvent on the complexes was then studied using a model with a spherical cavity surrounded by a dielectric continuum. Since the cis forms of the complexes have large dipole moments, the dipole term of the solvent reaction field strongly favours these structures. However, it is found that the quadrupolar terms have an almost equally large effect in the opposite direction, favouring the trans isomer. Even the octapole and hexadecapole moments make non-negligible contributions to the relative stabilities.Keywords
This publication has 31 references indexed in Scilit:
- Modeling the Solvent Sphere: Mechanism of the Shilov ReactionJournal of the American Chemical Society, 1996
- An Unusual Type of H.cntdot..cntdot..cntdot.H Interaction: Ir-H.cntdot..cntdot..cntdot.H-O and Ir-H.cntdot..cntdot..cntdot.H-N Hydrogen Bonding and Its Involvement in .sigma.-Bond MetathesisJournal of the American Chemical Society, 1994
- Liquid-State Quantum Chemistry: An Improved Cavity ModelThe Journal of Physical Chemistry, 1994
- The bonding in second row transition metal dihydrides, difluorides and dichloridesTheoretical Chemistry Accounts, 1994
- A new type of intramolecular H ⋯ H ⋯ H interaction involving N–H ⋯ H(Ir)⋯ H–N atoms. Crystal and molecular structure of [IrH(η1-SC5H4NH)2(η2-SC5H4N)(PCy3)]BF4·0.72CH2Cl2Journal of the Chemical Society, Chemical Communications, 1994
- Water exchange of trans-dichlorodiaquaplatinum(II) and tetraaquaplatinum(II) studied by an oxidative-addition quenching technique. Isotopic shifts and platinum-195 NMR chemical shifts for mixed chloro-aqua complexes of platinum(II) and platinum(IV)Inorganic Chemistry, 1989
- Proton transport in water modeled by a quantum chemical dielectric cavity modelThe Journal of Physical Chemistry, 1988
- Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitalsThe Journal of Chemical Physics, 1985
- Polarisabilites moléculaires et effet diélectrique de milieu à l'état liquide. Étude théorique de la molécule d'eau et de ses diméresTheoretical Chemistry Accounts, 1973
- Volumen und Hydratationswärme der IonenThe European Physical Journal A, 1920