Theoretical analysis of bis(ethylene) complexes of molybdenum and tungsten

Diego del Río, G. Schubert, I. Pápai, Agustín Galindo

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Density functional calculations on the zero-valent bis(ethylene) and the actual trans-[M(C2H4)2 (PMe3)4] (M = Mo, W) compounds were carried out at the BPW91 level of theory. The experimentally characterised molecular structures of both molybdenum and tungsten complexes were properly reproduced by the energy optimised geometries only when the trimethylphosphine ligands were used. The experimentally observed ruffling of the phosphine ligands was not detected when the simplified model was considered. This discrepancy was interpreted as a consequence of different steric interactions between the PH3 and PMe3 ligands. The theoretical analysis gives a good account of some chemical properties observed in these compounds. In particular, the low PMe3 dissociation energies calculated for these compounds are in agreement with the experimental observation of free phosphine dissociation in the solutions of trans-[M(C2H4)2 (PMe3)4] compounds. The comparison of energy data for PH3 and PMe3 complexes corroborates the experimental hypothesis that phosphine dissociation has a steric origin.

Original languageEnglish
Pages (from-to)83-90
Number of pages8
JournalJournal of Organometallic Chemistry
Volume663
Issue number1-2
DOIs
Publication statusPublished - Dec 2 2002

Fingerprint

phosphine
Tungsten
Molybdenum
phosphines
molybdenum
Ethylene
tungsten
ethylene
Ligands
dissociation
ligands
Molecular Structure
chemical properties
Chemical properties
Molecular structure
Density functional theory
energy
molecular structure
Observation
Geometry

Keywords

  • DFT calculations
  • Ethylene complexes
  • Molybdenum
  • Tungsten

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Theoretical analysis of bis(ethylene) complexes of molybdenum and tungsten. / del Río, Diego; Schubert, G.; Pápai, I.; Galindo, Agustín.

In: Journal of Organometallic Chemistry, Vol. 663, No. 1-2, 02.12.2002, p. 83-90.

Research output: Contribution to journalArticle

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