Structure, EPR and UV-VIS and IR spectroelectrochemistry of reversibly reducible compounds (C5Me5)IrCl(L)(PF6), L= 1,3-dimethyllumazine or 1,3-dimethylalloxazine

, , , und . Journal of the Chemical Society, Faraday Transactions 92 (21): 4233--4238 (1996)


In an attempt to model possible metal-pterin or metal-flavin ligand interactions (C5Me5)IrCl(L)(PF6) (L= 1,3-dimethyllumazine or 1,3-dimethylalloxazine) were prepd. and their structure, spectroscopy and spectroelectrochem. (EPR, IR, UV-visible) compared with results for the corresponding Rh analogs. The x-ray crystal structure of (C5Me5)IrCl(DML)(PF6), DML = 1,3-dimethyllumazine, shows O4/N5 chelate coordination of Ir with a shorter bond to the N center 2.103(4) vs. 2.186(3) \AA, a slightly more unsym. situation than that found in the Rh analog. Electrochem. studies (cyclic voltammetry, polarog.) showed largely reversible 1-electron redn. processes to radical species (C5Me5)IrCl(L).bul. which allowed the authors to study the EPR, IR and UV-visible response to the redn. Although the EPR spectra of the Ir compds. remained unresolved, the low g factors (g\textless2) and particular line shapes revealed small but significant contributions from the heavy-metal center. Long-wavelength absorptions at $\sim$600 nm and low-energy shifts of the carbonyl stretching bands confirm the formulation (C5Me5)IrIIICl(L-I).bul. for the electronic situation. on SciFinder(R)

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