Binding of ethylene to platinum and palladium. An ab initio study of the MCl/sub 3/(C/sub 2/H/sub 4/)/sup -/ species
The structures and bonding of the metal-olefin ..pi..-complexes PtCl/sub 3/(C/sub 2/H/sub 4/)/sup -/ and PdCl/sub 3/(C/sub 2/H/sub 4/)/sup -/ are investigated with ab initio calculations in an extended basis. Relativistic effective core potentials are employed on Pd and Pt to replace the core electrons and to incorporate the relativistic effects on the valence electrons. The optimized geometries of the Pt-C/sub 2/H/sub 4/ and Pd-C/sub 2/H/sub 4/ complexes are discussed and compared with the structure determined by neutron diffraction for KPtCl/sub 3/(C/sub 2/H/sub 4/). The calculated barrier to rotation in Zeise's salt (15 kcal/mol) is in good agreement with observed barriers (10 to 14 kcal) in platinum-olefin complexes. The barriers to rotation and binding energies both decrease in the order Pt > Pd. The results are compared to the Dewar-Chatt-Duncanson model of metal-olefin bonding.
- Research Organization:
- Los Alamos Scientific Lab., NM
- OSTI ID:
- 6342030
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 103:6
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ETHYLENE
BOND LENGTHS
CHEMICAL BONDS
PALLADIUM COMPLEXES
PLATINUM COMPLEXES
BINDING ENERGY
CHLORIDES
COMPARATIVE EVALUATIONS
LIGANDS
NEUTRON DIFFRACTION
ORGANOMETALLIC COMPOUNDS
ROTATIONAL STATES
STRUCTURAL CHEMICAL ANALYSIS
THEORETICAL DATA
ALKENES
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
DIMENSIONS
ENERGY
ENERGY LEVELS
EXCITED STATES
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
INFORMATION
LENGTH
NUMERICAL DATA
ORGANIC COMPOUNDS
SCATTERING
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)