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The electroactive species in the catalysis of cyclohexadiene to benzene by Rh2(TM4) +24 (TM4=2,5-diisocyano-2,5-dimethylhexane)

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Abstract

Upon further investigation of the recently reported electrocatalytic oxidation of 1,4-cyclohexadiene to benzene by Rh2(TM4) +24 (TM4=2,5-diisocyano-2,5-dimethylhexane), we have obtained data which strongly implicates the 2e− oxidized d7-d7 complex as the electroactive species. This contrasts with the original report which suggested that the le− oxidized d7-d8 radical acted as the key species via hydrogen atom abstraction from 1,4-cyclohexadiene. A possible mechanism for the catalysis is proposed.

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  10. Attempts to generate solutions of Rh2(TM4)4(PF6) +22 from large-scale bulk electrolysis of [Rh2(TM4)4][PF6]2 in 0.1M TBA+PF }6 /CH2C12 resulted the considerable decomposition of the rhodium-containing species due to the instability of Rh2(TM4)4(PF6) +22 over long periods of time.

  11. The cyclic voltammogram of Rh2(TM4) +24 in 0.1M TBA+C1O4 exhibits a quasi-reversible 2e− oxidation. At 25 °C, K′disp=18 [3]. Addition of 1,4-cyclohexadiene to this solution causes only a slight anodic current enhancement; however, exhaustive bulk electrolysis past the Rh2(TM4)4(ClO4) +22 /Rh2(TM4) +24 couple turns the catalysis over an average of 5 times.

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  1. Contribution from the Department of Chemistry, University of Minnesota, 55455, Minneapolis, Minnesota, USA

    Michael G. Hill & Kent R. Mann

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  1. Michael G. Hill
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  2. Kent R. Mann
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Hill, M.G., Mann, K.R. The electroactive species in the catalysis of cyclohexadiene to benzene by Rh2(TM4) +24 (TM4=2,5-diisocyano-2,5-dimethylhexane). Catal Lett 11, 341–347 (1991). https://doi.org/10.1007/BF00764326

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  • DOI: https://doi.org/10.1007/BF00764326

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