pi effects involving Rh-PZ(3) compounds. The quantitative analysis of ligand effects (QALE)

M R Wilson, A Prock, W P Giering, A L Fernandez, C M Haar, Steven Patrick Nolan, B M Foxman

Research output: Contribution to journalArticlepeer-review

55 Citations (Scopus)

Abstract

Through the quantitative analysis of ligand effects (QALE), we have probed pi effects associated with Rh-P bond lengths, nu(CO), and -DeltaH(rx) for Rh(CO)(Cl)(PX3)(2) and nu(CO) and -DeltaH(rx) for Rh(acac)(CO)(PZ(3)). It was found that pi effects are complex and depend strongly on the nature of ancillary or other participatory groups. The results of the QALE analysis of -DeltaH(rx) point out the importance of synergistic interactions between PZ3 and other ancillary ligands in accord with theoretical computations. Literature data for Rh(CO)(Cl)(PZ3)2 have been supplemented with new values of DeltaH(rx) for PMe3 (-75.6 +/- 0.3 kcal/mol), P(i-Pr)(3) (-68.7 +/- 0.3 kcal/mol), and PCy3 (-66.4 +/- 0.4 kcal/mol) as well as crystal structures for Rh(CO)(Cl)(P(i-Pr-3))(2) (Rh-P = 2.34880 Angstrom) and Rh(CO)(Cl)(PCy3)(2) (Rh-P = 2.3508(3)).

Original languageEnglish
Pages (from-to)2758-2763
Number of pages6
JournalOrganometallics
Volume21
Issue number13
DOIs
Publication statusPublished - 24 Jun 2002

Keywords

  • TERTIARY PHOSPHINE LIGAND
  • N-PYRROLYL PHOSPHINES
  • STEREOELECTRONIC PARAMETERS
  • REORGANIZATION ENERGIES
  • SUBSTITUTION-REACTIONS
  • ACCEPTOR CHARACTER
  • COMPLEXES
  • RHODIUM
  • BOND
  • CRYSTAL

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