Spin selectivity in the oxygenation of singlet phenylhalocarbenes with oxygen

Makihara, Taiki; Nojima, Takayuki; Ishiguro, Katsuya; Sawaki, Yasuhiko

doi:10.1016/s0040-4039(02)02538-8

Cited by 8 publications

(11 citation statements)

References 36 publications

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“…If solvent effects were not influential, the present results would ratify the interpretation offered in [1]. If solvent effects were not influential, the present results would ratify the interpretation offered in [1].…”

Section: Resultssupporting

confidence: 77%

“…However, the reactions of PHC with O 2 ( 3 Σ g − ) to yield carbonyl oxides are smooth, while reactions with the singlet spin state of the oxygen are relatively slow [1]. However, the reactions of PHC with O 2 ( 3 Σ g − ) to yield carbonyl oxides are smooth, while reactions with the singlet spin state of the oxygen are relatively slow [1].…”

Section: Oxygenation Reaction: Modelsmentioning

confidence: 99%

“…In [1], solution reactions involving six different compounds were investigated, where (X,Y)-as noted in Scheme 1-were (Cl,H), (Br,H), (F, NO 2 ), (Cl,NO 2 ) and (Br,NO 2 ) compounds. In [1], solution reactions involving six different compounds were investigated, where (X,Y)-as noted in Scheme 1-were (Cl,H), (Br,H), (F, NO 2 ), (Cl,NO 2 ) and (Br,NO 2 ) compounds.…”

Section: Oxygenation Reaction: Modelsmentioning

confidence: 99%

“…Spin selectivity experiments in solution for the oxygenation of spin-singlet phenylhalocarbenes (PHCs) with spin-triplet state dioxygen have been reported by Makihara et al and interpreted by performing in vacuo DFT calculations [1]. In solution, these reactions are kinetically slow but exothermic.…”

Section: Introductionmentioning

confidence: 99%

“…In view of the limited computational scope reported in [1], it is apparent that there is room for a more detailed theoretical study of possible reaction mechanisms in vacuum; this includes calculations of potential energy profiles, as well as reactivity descriptors that suggest local properties which global energy descriptors normally miss. This work is a step toward the combination of global and local quantities related to reactivity issues.…”

Section: Introductionmentioning

confidence: 99%

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Oxygenation of the phenylhalocarbenes. Are they spin-allowed or spin-forbidden reactions?

et al. 2011

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Oxygenation mechanisms of phenylhalocarbenes in vacuum are investigated through the use of density functional theory and CASSCF-PT2 approaches. Reactions with both substituted and unsubstituted phenylhalocarbenes are strongly exothermic. The reactions with nitrosubstituted halocarbenes are predicted to be spin allowed due to the practical degeneracy of the singlet and triplet carbene states. Conversely, for the unsubstituted compounds, the equilibrium between the triplet carbene and (3)O(2) requires a previous singlet-triplet state crossing. The large spin-orbit coupling at this crossing suggests a rather efficient tunneling rate. This would help to explain why the rate constant in solution in these cases is only one order of magnitude smaller than those involving a spin-allowed process. Moreover, the action of the solvent as a third body appears to play a fundamental role in prompting relatively smooth rates.

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Section: Resultssupporting

confidence: 77%

Section: Oxygenation Reaction: Modelsmentioning

confidence: 99%