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Titolo:
Ab initio calculations on cis-[PtCl2(PMe3)(2)]: Search for a model chemistry for platinum(II) complexes
Autore:
Kozelka, J; Berges, J;
Indirizzi:
Chimanceiochim Pharmacol & Toxicol Lab, CNRS, URA 400, F-75270 Paris 06, Fr Chim & Biochim Pharmacol & Toxicol Lab Paris France 06 5270 Paris 06, Fr Univ Paris 06, Chim Theor Lab, F-75005 Paris, France Univ Paris 06 ParisFrance F-75005 Chim Theor Lab, F-75005 Paris, France
Titolo Testata:
JOURNAL DE CHIMIE PHYSIQUE ET DE PHYSICO-CHIMIE BIOLOGIQUE
fascicolo: 10, volume: 95, anno: 1998,
pagine: 2226 - 2240
Fonte:
ISI
Lingua:
ENG
Soggetto:
EFFECTIVE CORE POTENTIALS; METAL DIHYDROGEN COMPLEXES; DENSITY-FUNCTIONAL THEORY; MOLECULAR CALCULATIONS; TRANS-INFLUENCE; HARTREE-FOCK; BONDS; ATOMS; OPTIMIZATION; PHOSPHINE;
Keywords:
platinum complexes; Hartree-Fock calculations; density functional theory; Moller-Plesset perturbation theory; dipole moment; trans-influence;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
54
Recensione:
Indirizzi per estratti:
Indirizzo: Kozelka, J Chim5270iochim Pharmacol & Toxicol Lab, CNRS, URA 400, 45 Rue St Peres, F-7 Chim & Biochim Pharmacol & Toxicol Lab 45 Rue St Peres Paris France 06
Citazione:
J. Kozelka e J. Berges, "Ab initio calculations on cis-[PtCl2(PMe3)(2)]: Search for a model chemistry for platinum(II) complexes", J CHIM PHYS, 95(10), 1998, pp. 2226-2240

Abstract

The capacity of Hartree-Fock (HF), Moller-Plesset second order perturbation (MP2), and density functional (DF) calculations to predict the experimental dipole moment and the metal-ligand bond lengths of a planar platinum(II)complex, cis[PtCl2(PMe3)(2)], was investigated. Highly erroneous results were obtained from uncorrelated HF calculations and from MP2 and DF calculations which included the 5s and 5p electrons of platinum in a frozen core orin an effective core potential. DF calculations including these (n-1)s and(n-1)p electrons in the valence space are shown to have the ability to correctly reproduce the platinum-ligand bond lengths and the dipole moment, provided that sufficiently large basis sets including polarization functions are used. MP2 calculations yielded dipole moments comparable to those obtained from DF calculations with the same basis set and reproduced better the difference between the Pt-Cl and Pt-P bond lengths, but required 2-6 times more computer time. The best agreement between calculated and experimental dipole moment and bond length values was obtained with DF calculations using the program ADF, provided that the scalar relativistic terms were included in the hamiltonian. Our results indicate that the mutual influence of theplatinum-ligand bonds in trans-position (the so-called trans-influence) involves both electron correlation and relativistic effects.

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Documento generato il 10/07/20 alle ore 00:14:04