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

Lionel Perrin (1) , Eric Clot (1) , Odile Eisenstein (1) , Jennifer Loch (2) , Robert H. Crabtree (2)

1 LSDSMS - Laboratoire de structure et de dynamique des systèmes moléculaires et solides
2 Department of Chemistry [New Haven]

The calculated (DFT, B3PW91) A(1) v(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.

Mots clés: SIGMA; CO; MO; ELECTROCHEMICAL PARAMETRIZATION; METAL-CARBONYLS; ORGANOMETALLIC CHEMISTRY; VIBRATIONAL-SPECTRA; PHOSPHORUS LIGANDS; KINETICS; ENERGY

Domaines: Chimie-Physique [physics.chem-ph]

Lionel Perrin, Eric Clot, Odile Eisenstein, Jennifer Loch, Robert H. Crabtree. Computed ligand electronic parameters, from quantum chemistry and their relation to Tolman parameters, Lever parameters, and Hammett constants. Inorganic Chemistry, 2001, 40, pp.5806-5811. ⟨10.1021/ic0105258⟩. ⟨hal-00429103⟩