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Royal Society of Chemistry

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New Journal of Chemistry

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The binding of carbon monoxide to carbon centers has been examined with two series of aromatic and aliphatic oxocarbonium ions that are successfully isolated as crystalline and highly reactive (hygroscopic) aroylium and acylium salts with poorly coordinating counteranions. X-Ray crystallographic analyses at −150 °C afford precise structural parameters for the characteristic linear carbonyl bond (rCO) and the bond to the carbon centers (r). The correlations of these structural parameters evaluated for alkyl (Me, Et and i-Pr) and aryl (p-Me, 2,4,6-trimethyl, p-MeO and p-fluorophenyl) oxocarbonium ions with the corresponding carbonyl stretching frequencies in the solid-state (reflectance) IR spectra yield valuable insight into the binding mode of carbon monoxide. Most noteworthy is the synergic (π–σ) bonding in aroylium structures in contrast to the mainly σ bonding in acylium structures that are organic mimics for carbon monoxide bonding in classical and nonclassical metal carbonyls, respectively.


Accepted version. New Journal of Chemistry, No. 28 (2004): 1568-1574. DOI. © 2004 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique. Used with permission.

Sergey V. Lindeman was affiliated with the University of Houston at the time of publication.

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