π Effects Involving Rh−PZ₃ Compounds. The Quantitative Analysis of Ligand Effects (QALE)

Authors

Matthew R. Wilson
Alfred Prock
Warren P. Giering
Anthony L. Fernandez, Merrimack CollegeFollow
Christopher M. Haar
Steven P. Nolan
Bruce M. Foxman

Document Type

Article - Merrimack Access Only

Publication Title

Organometallics

Publication Date

5-2002

Abstract/ Summary

Through the quantitative analysis of ligand effects (QALE), we have probed π effects associated with Rh-P bond lengths, ν_CO, and -∆H_rx for Rh(CO)(Cl)(PX₃)₂ and ν_CO and -∆H_rx for Rh(acac)(CO)(PZ₃). It was found that π effects are complex and depend strongly on the nature of ancillary or other participatory groups. The results of the QALE analysis of -∆H_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 ∆H_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-Pr₃))₂ (Rh-P ) 2.3488(3) Å) and Rh(CO)(Cl)(PCy₃)₂ (Rh-P ) 2.3508(3)).

Repository Citation

Wilson, M. R., Prock, A., Giering, W. P., Fernandez, A. L., Haar, C. M., Nolan, S. P., & Foxman, B. M. (2002). π Effects Involving Rh−PZ₃ Compounds. The Quantitative Analysis of Ligand Effects (QALE). Organometallics, 21(13), 2758-2763.
Available at: https://scholarworks.merrimack.edu/chm_facpub/4