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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 atropoisomeric diphosphanes, we show how coordination geometry can switch the carbonyl stretching frequency into a selective probe of the σ-donor and π-acceptor abilities of the ligands. We thus provide a framework whereby the σ-donation and π-backdonation constituents of the Dewar-Chatt-Duncanson model can be quantitatively predicted through spectroscopic data on coordinated CO moieties and vice versa.

chemical communications

Exploiting coordination geometry to selectively predict the σ-donor and π-acceptor abilities of ligands: a back-and-forth journey between electronic properties and spectroscopy