Mechanism and product characterization from the electroreduction of heterodinuclear complexes (C5Me5)ClM(m-L)Re(CO)3X(PF6), M = Rh or Ir, L = 2,2'-azobispyridine or 2,2'-azobis(5-chloropyrimidine), X = halide

, , , , , und . Inorganica Chimica Acta 357 (10): 2905--2914 (2004)


The title compds. are easily reduced to paramagnetic neutral species (C5Me5)ClM(m-L)Re(CO)3X.bul. which were characterized as complexes of L.bul.-. On further electron addn. the M-bound chloride is dissocd. slowly to yield (C5Me5)M(m-L)Re(CO)3X, distinguished by intense low-energy charge transfer bands. Addn. of a 3rd electron causes this band to shift and diminish in intensity. Cyclic voltammetry, UV-visible-NIR and IR spectroelectrochem. as well as EPR at 9.5 and 285 GHz were used to establish the (E, EC, E) process sequence of electroredn. and to identify the products. The significance of these results for potential applications in catalysis is discussed. on SciFinder(R)

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