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- W2003251011 abstract "The decomposition reactions of hydroperoxides (ROOH) by sulfonium compounds or some nucleophiles (sulfides, phosphites, and transition metal ions) were treated by the extended Hückel method, augmented by the use of d-orbitals. We obtained serveral findings. First, ROOH was more reactive to nucleophiles and was energetically more stable than (ROOH)2. Second, the order of the ability for the ROOH decomposition, sulfonium compounds>>sulfides>phosphitesgtrsimthiophene, was in good agreement with that of the AO populations of the nonbonding lone pair orbitals of the above compounds. Third, the distinguished ability of the sulfonium compound may be attributed to the contribution of the partially-occupied sulfur d-orbitals, in particular, the lowest unoccupied dz2-orbital; in the ROOH decomposition, these orbitals interact with the lowest unoccupied antibonding pσ-orbital of the O–O in ROOH at the Oβ atom in the direction of the O–O axis. Finally, it was concluded that the sulfur d-orbitals contribute to the long-range interaction (S–Oβ>3.0 Å) between ROOH and sulfonium compounds." @default.
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- W2003251011 date "1972-02-01" @default.
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- W2003251011 title "An MO-Theoretical Study of the Decomposition of Hydroperoxides by Sulfonium Compounds and Some Nucleophiles" @default.
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- W2003251011 doi "https://doi.org/10.1246/bcsj.45.322" @default.
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