The electrochemical response of bis-Co2C2(CO)(4)(mu-dppm) complexes featuring bridging para-CB10H10C (5) and para-C6H4 (6) moieties are similar, each exhibiting two oxidations separated by ca. 100 mV, and two reductions separated by 80 mV, evidencing a degree of "electronic communication". A computational study of these systems and of the butadiyndiyl-bridged species (7) reveals an increasing contribution from the bridge pi-orbitals in the frontier MO's of the monocations 5(+) < 6(+) < 7(+). Thus, while similar conclusions about electronic interactions between the cluster-based redox probes through the cluster or organic bridges may be drawn from electrochemical studies, the mechanism by which these effects transmitted is subtly different in each case.
Electronic interactions in bridged bis(cluster) assemblies - a comparison of para-CB10H10C, para-C6H4 and C-4 bridges
NERVI, Carlo;
2005-01-01
Abstract
The electrochemical response of bis-Co2C2(CO)(4)(mu-dppm) complexes featuring bridging para-CB10H10C (5) and para-C6H4 (6) moieties are similar, each exhibiting two oxidations separated by ca. 100 mV, and two reductions separated by 80 mV, evidencing a degree of "electronic communication". A computational study of these systems and of the butadiyndiyl-bridged species (7) reveals an increasing contribution from the bridge pi-orbitals in the frontier MO's of the monocations 5(+) < 6(+) < 7(+). Thus, while similar conclusions about electronic interactions between the cluster-based redox probes through the cluster or organic bridges may be drawn from electrochemical studies, the mechanism by which these effects transmitted is subtly different in each case.
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