Photochemistry of electron donor-acceptor complexes of the bis(fulvalene) dicobalt mono- and dications

S. F. Clark, R. J. Watts, Daniel L DuBois, J. s. Connolly, J. C. Smart

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Abstract

Addition of carbon tetrachloride or chloroform to acetonitrile solutions of the bis(fulvalene)dicobalt monocation results in the appearance of new absorption features which are attributed to formation of electron donor-acceptor complexes. The association constants of these complexes aer 2.36 /mole fraction (carbon tetrachloride) and 2.74 /mole fraction (chloroform). Excitation in the absorption bands of the donor-acceptor complexes results in oxidation of the monocation to the dication with high quantum yields. A donor-acceptor complex is also formed when sodium tetraphenylborate is added to acetonitrile solutions of the bis(fulvalene)dicobalt dication. Spectroscopic determination of the association constant of the dication with tetraphenylborate yields a value of 26.3 /mole fraction. Excitation of the absorption bands of the ion-pair results in high quantum yields for formation of the bis(fulvalene) dicobalt monocation. Biphenyl is found in photolyzed solutions as a byproduct of the oxidation of the tetraphenylborate anion.

Original languageEnglish
Pages (from-to)273-292
Number of pages20
JournalCoordination Chemistry Reviews
Volume64
Issue numberC
DOIs
Publication statusPublished - 1985

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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