Through an analysis of eighty tetrahedral and square-planar metal carbonyls of general formula [M(CO)(L')(L)(2)] including newly synthesized chlorocarbonyl rhodium complexes with chelating atropo-isomeric diphosphanes, we show how coordination geometry can switch the carbonyl stretching frequency into a selective probe of the sigma-donor and pi-acceptor abilities of the ligands. We thus provide a framework whereby the sigma-donation and pi-backdonation constituents of the Dewar-Chatt-Duncanson model can be quantitatively predicted through spectroscopic data on coordinated CO moieties and vice versa.
Exploiting coordination geometry to selectively predict the r-donor and p-acceptor abilities of ligands: a back-and-forth journey between electronic properties and spectroscopy / M. Fuse`, I. Rimoldi, G. Facchetti, S. Rampino, V. Barone. - In: CHEMICAL COMMUNICATIONS. - ISSN 1359-7345. - 54:9(2018 Feb 07), pp. 2397-2400.
Exploiting coordination geometry to selectively predict the r-donor and p-acceptor abilities of ligands: a back-and-forth journey between electronic properties and spectroscopy
I. RimoldiSecondo
;G. Facchetti;
2018
Abstract
Through an analysis of eighty tetrahedral and square-planar metal carbonyls of general formula [M(CO)(L')(L)(2)] including newly synthesized chlorocarbonyl rhodium complexes with chelating atropo-isomeric diphosphanes, we show how coordination geometry can switch the carbonyl stretching frequency into a selective probe of the sigma-donor and pi-acceptor abilities of the ligands. We thus provide a framework whereby the sigma-donation and pi-backdonation constituents of the Dewar-Chatt-Duncanson model can be quantitatively predicted through spectroscopic data on coordinated CO moieties and vice versa.File | Dimensione | Formato | |
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