The relation between spectroscopic observables and the detailed metal- ligand bonding features in chelation complexes is addressed using both experimental and state-of-the-art theoretical and computational methods. We synthesized and characterized a set of six nickel dicarbonyl complexes of general formula [Ni(CO)(2)(PP)], where PP is an atropoisomeric chelating diphosphine ligand. The analysis of the obtained experimental data and the basicity and oxidative potentials of the free ligands suggests a close relation between the donor ability of the chelating ligand and the carbonyl stretching frequencies observed in the complexes. We then use theory to unravel the detailed mechanisms of chelation-bond formation in terms of partial charge flows between the molecular orbitals of the fragments. By extending the promising, recently published natural orbitals for chemical valence/ charge displacement (NOCV/CD) analysis scheme we provide a thorough, quantitative description of the several charge fluxes following the metal-ligand bond formation and demonstrate that the carbonyl stretching frequencies in the considered complexes selectively respond to the sigma-donation charge flow from the phosphorus lone pairs of the ligands, with the frequency shift being in quantitative correlation with the extent of the ligand-to-metal charge transfer.
On the relation between carbonyl stretching frequencies and the donor power of chelating diphosphines in nickel dicarbonyl complexes / M. Fusè, I. Rimoldi, E. Cesarotti, S. Rampino, V. Barone. - In: PHYSICAL CHEMISTRY CHEMICAL PHYSICS. - ISSN 1463-9084. - 19:13(2017 Apr 07), pp. 9028-9038.
|Titolo:||On the relation between carbonyl stretching frequencies and the donor power of chelating diphosphines in nickel dicarbonyl complexes|
|Settore Scientifico Disciplinare:||Settore CHIM/03 - Chimica Generale e Inorganica|
Settore CHIM/02 - Chimica Fisica
|Data di pubblicazione:||7-apr-2017|
|Data ahead of print / Data di stampa:||5-mar-2017|
|Digital Object Identifier (DOI):||http://dx.doi.org/10.1039/c7cp00982h|
|Appare nelle tipologie:||01 - Articolo su periodico|
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