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-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...

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Published inInorganic chemistry Vol. 41; no. 14; pp. 3590 - 3592
Main Authors Hanna, Tracy A, Rieger, Anne L, Rieger, Philip H, Wang, Xiaoyu
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 15.07.2002
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Abstract 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.
AbstractList The reaction of BiCl(3) 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)Pr(2)C(6)H(3))(3) and ClBi(O-2,4,6-(t)Bu(3)C(6)H(2))(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.
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.
Author Hanna, Tracy A
Wang, Xiaoyu
Rieger, Philip H
Rieger, Anne L
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Snippet 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,...
The reaction of BiCl(3) with the lithium salt of o-di-tert-butylphenol under nitrogen forms organic oxidation products rather than the expected Bi(OAr)(3)...
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Title Evidence for an Unstable Bi(II) Radical from Bi−O Bond Homolysis. Implications in the Rate-Determining Step of the SOHIO Process
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