Computed ligand electronic parameters from quantum chemistry and their relation to Tolman parameters, Lever parameters, and Hammett constants

L Perrin; E Clot; O Eisenstein; J Loch; R H Crabtree

doi:10.1021/ic0105258

Computed ligand electronic parameters from quantum chemistry and their relation to Tolman parameters, Lever parameters, and Hammett constants

Inorg Chem. 2001 Nov 5;40(23):5806-11. doi: 10.1021/ic0105258.

Authors

L Perrin¹, E Clot, O Eisenstein, J Loch, R H Crabtree

Affiliation

¹ Laboratoire de Structure et Dynamique des Systèmes Moléculaires et Solides, UMR 5636 (CNRS), Université de Montpellier 2, 34095 Montpellier Cedex 5, France.

PMID: 11681889
DOI: 10.1021/ic0105258

Abstract

The calculated (DFT, B3PW91) A(1) nu(CO) frequency in LNi(CO)(3) defines an electronic parameter that reliably predicts the relative donor powers of a wide variety of cationic, neutral, and negatively charged ligands. These calculated parameters correlate very well with the available Tolman and Lever parameters, and also with Hammett's sigma(m), where available. The method avoids any experimental limitations and, in particular, can be used for proposed ligands not yet experimentally available.