Evidence for an Unstable Bi(II) Radical from Bi−O Bond Homolysis. Implications in the Rate-Determining Step of the SOHIO Process

• Published in: Inorganic chemistry Vol. 41; no. 14; pp. 3590 - 3592
• Main Authors: Hanna, Tracy A, Rieger, Anne L, Rieger, Philip H, Wang, Xiaoyu
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 15.07.2002
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic0202864

The reaction of BiCl3 with the lithium salt of o-di-tert-butylphenol 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- i Pr2C6H3)3 and ClBi(O-2,4,6- t Bu3C6H2)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.