Linear versus bent bonding in metal-phosphinidene complexes: Theoretical studies of the electrophilic phosphinidene complexes [(Cp)(CO)<inf>2</inf>M{triple bond, long}PMe)]<sup>+</sup>, [(Cp)(CO)<inf>3</inf>M{double bond, long}PMe)]<sup>+</sup> (M = Cr, Mo, W)

Krishna K. Pandey, Agustí Lledós

Research output: Contribution to journalArticleResearchpeer-review

13 Citations (Scopus)

Abstract

Density functional theory calculations have been performed for the title phosphinidene complexes using the exchange correlation functionals BP86 and B3LYP. The optimized bond lengths and angles of the model compounds are in excellent agreement with experiment. The M-P bond lengths in linear phosphinidene complexes correspond to a Pauling bond order of ∼ 3. The bent geometries at phosphorus in the bent metal phosphinidene complexes are consistent with the presence of a trivalent phosphorus(III) center which is singly bonded to carbon and doubly bonded to transition metal. The analysis of the delocalized Kohn-Sham orbitals shows the polarization of the M-P σ bonding orbitals towards the phosphorus atom in the M{triple bond, long}PMe bonds, while in the M{double bond, long}PMe bond, the contributions of metal and phosphorus are almost the same. In the linear phosphinidene complexes the contributions of the covalent bonding ΔEorb are more than the electrostatic interaction ΔEelstat. The bent phosphinidene complexes have a lower degree of covalent bonding than the linear phosphinidene complexes. The major differences between the linear and bent phosphinidene complexes are found in the degree of π-bonding. The M{triple bond, long}PMe bonds show a true M-P π bond and a deviated π bond due to slight bent M-P-C bond angles. The M{double bond, long}PMe bonds show a true M-P π bond and a lone-pair on phosphorus. © 2009 Elsevier B.V. All rights reserved.
Original languageEnglish
Pages (from-to)206-214
JournalJournal of Organometallic Chemistry
Volume695
Issue number2
DOIs
Publication statusPublished - 15 Jan 2010

Keywords

  • DFT
  • Energy decomposition analysis
  • Metal-phosphinidene bonding
  • Structure

Fingerprint Dive into the research topics of 'Linear versus bent bonding in metal-phosphinidene complexes: Theoretical studies of the electrophilic phosphinidene complexes [(Cp)(CO)<inf>2</inf>M{triple bond, long}PMe)]<sup>+</sup>, [(Cp)(CO)<inf>3</inf>M{double bond, long}PMe)]<sup>+</sup> (M = Cr, Mo, W)'. Together they form a unique fingerprint.

Cite this