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.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry