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Intermolecular-directed reactivity in solid media. Radiogenic formation of phosphorus-centered radicals in chiral diphosphine disulfides studied by ESR

Aagaard, Olav M ; Janssen, Rene A. J ; De Waal, Bas F. M ; Kanters, Jan A ; Schouten, Arie ; Buck, Henk M

Journal of the American Chemical Society, , Vol.112 (14), p.5432-5447 [Periódico revisado por pares]

Washington, DC: American Chemical Society

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Título:
Intermolecular-directed reactivity in solid media. Radiogenic formation of phosphorus-centered radicals in chiral diphosphine disulfides studied by ESR
Autor: Aagaard, Olav M ; Janssen, Rene A. J ; De Waal, Bas F. M ; Kanters, Jan A ; Schouten, Arie ; Buck, Henk M
Assuntos: Atomic and molecular physics ; CHEMISTRY ; DATA ; DATA ANALYSIS ; DISULFIDES ; Exact sciences and technology ; EXPERIMENTAL DATA ; INFORMATION ; MEASURING INSTRUMENTS ; MEASURING METHODS ; Molecular properties and interactions with photons ; NUMERICAL DATA ; ORGANIC COMPOUNDS ; ORGANIC PHOSPHORUS COMPOUNDS ; ORGANIC SULFUR COMPOUNDS ; PHYSICAL RADIATION EFFECTS ; Physics ; RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY ; RADIATION EFFECTS 400600 -- Radiation Chemistry ; RADICALS ; RADIOCHEMISTRY
É parte de: Journal of the American Chemical Society, , Vol.112 (14), p.5432-5447
Notas: ark:/67375/TPS-9JW9680P-3
istex:0F9E020811EA2F624640FDAFF22BEE656E764420
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Descrição: Single-crystal, powder, and frozen-matrix ESR experiments have been performed to study the radiogenic electron-capture properties of several diastereoisomeric and asymmetric diphosphine disulfides (R{sub 1}R{sub 2}P(S)P(S)R{sub 3}R{sub 4}). The principal values of the hyperfine couplings of several phosphorus-centered radical configurations are determined and related to the spin density distribution. Attention is focused on the strong differences in radiogenic properties, observed between the meso and racemic forms of phenyl- and tolyl-substituted diphosphine disulfides. The most striking result is that X irradiation of the crystalline meso compounds MePhP(S)P(S)MePh, Me(p-Tol)P(S)P(S)Me(p-Tol), and Ph(PhCH{sub 2})P(S)P(S)Ph(CH{sub 2}Ph) does not lead to the formation of a three-electron bond P-P {sigma}* radical but invariably results in configurations in which the unpaired electron is primarily localized on one half of the molecule. X irradiation of the corresponding racemic forms, on the other hand, gives rise to P-P {sigma}* configurations.
Editor: Washington, DC: American Chemical Society
Idioma: Inglês

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Intermolecular-directed reactivity in solid media. Radiogenic formation of phosphorus-centered radicals in chiral diphosphine disulfides studied by ESR

Aagaard, Olav M ; Janssen, Rene A. J ; De Waal, Bas F. M ; Kanters, Jan A ; Schouten, Arie ; Buck, Henk M

Washington, DC: American Chemical Society

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