Journal ArticleDOI
Evidence for an unstable Bi(II) radical from Bi-O bond homolysis. Implications in the rate-determining step of the SOHIO process.
TLDR
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.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-iPr2C6H3)3 and ClBi(O-2,4,6-tBu3C6H2)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.read more
Citations
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From molecules to bismuth oxide-based materials: Potential homo- and heterometallic precursors and model compounds
TL;DR: In this article, a review of the potential of bismuth-containing heterometallic oxides is presented together with feasible applications of the latter, and a variety of structurally related high-nuclearity molecular Bismuth oxo clusters are discussed that serve as model compounds.
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The role of bismuth in the SOHIO process
TL;DR: In this article, it was shown that bismuth is involved in the rate-determining hydrogen abstraction from propene in both cases, and may be involved in later steps of the process as well.
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Facile bismuth-oxygen bond cleavage, C-H activation, and formation of a monodentate carbon-bound oxyaryl dianion, (C₆H₂(t)Bu₂-3,5-O-4)²⁻.
TL;DR: Structural, spectroscopic, and DFT studies and a comparison with the protonated analogue 4, which was obtained by treatment of 4 with [HNEt(3)][BPh(4)], suggest that 4 contains an oxyaryl dianion.
Journal ArticleDOI
Persistent Antimony‐ and Bismuth‐Centered Radicals in Solution
TL;DR: Persistent stibinyl and bismuthinyl radicals are synthesized by facile dissociation of the corresponding dimers with bulky substituents by NMR and UV/Vis spectroscopy and the thermodynamic parameters for the dissociation equilibria are estimated.
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Bismuth Redox Catalysis: An Emerging Main-Group Platform for Organic Synthesis
Hye-Won Moon,Josep. Cornellà +1 more
TL;DR: In this article , the authors provide an overview of the synthetic methodologies that have been developed to date, which capitalize on the Bi redox cycling, and discuss opportunities and future directions in this emerging field of catalysis.
References
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Surface intermediates in selective propylene oxidation and ammoxidation over heterogeneous molybdate and antimonate catalysts
TL;DR: In this paper, the influence of the ammonia/propylene feed ratio on the acrylonitrile/acrolein product ratio for bismuth molybdate-based catalysts indicates the presence of two mechanistic regimes.
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Nuclear magnetic resonance of organic free radicals
TL;DR: The conditions under which N.M.R. spectra of organic free radicals can be observed are discussed in this paper, where the sign and magnitude of the interaction between the unpaired electron and the nucleus are investigated.
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Formation of gas-phase .pi.-allyl radicals from propylene over bismuth oxide and .gamma.-bismuth molybdate catalysts
Wilson Martir,Jack H. Lunsford +1 more
TL;DR: In this article, gas-phase allyl radicals were produced when propylene reacted over Bi/sub 2/O/sub 3/ and Gamma..-bismuth molybdate catalysts at 723 K. The matrix was formed on a sapphire rod at 12 K which was located 33 cm downstream from the catalyst.