Evidence for an unstable Bi(II) radical from Bi-O bond homolysis. Implications in the rate-determining step of the SOHIO process

The reaction of BiCl3 with the lithium salt of o-di- tert-butyl phenol under nitrogen forms organic oxidation products rather than the expected Bi(OAr)(3) complex, and bismuth disproportionation products. Likewise, the decomposition of Bi(III) aryloxides Bi(O-2,6-(Pr2C6H3)-Pr-i)(3) and ClBi(O-2,4,6-(Bu3C6H2)-Bu-t)(3) leads to corresponding organic oxidation products. These reactions can be explained by Bi-O bond homolysis to form unstable Bi(II) radicals, analogous to a fundamental step suggested to intervene in the SOHIO process.