1974
DOI: 10.1021/ja00825a007
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Formation and reactions of monovalent carbon intermediates. III. Reaction of carbethoxymethyne with olefins

Abstract: Carbethoxymethyne (EtOCOC:) has been generated by the short wavelength photolysis of diethylmercury bisdiazoacetate, (N2CC02Et)2Hg + hv -* 2EtOCOC: + 2N2 + Hg, and its reactions with cyclohexene, c/s-2-butene, and rra«s-2-butene were investigated. The carbyne, formed in its 2 ground state, adds to the olefinic bond in a spin allowed but, according to INDO MO calculations, orbital symmetry forbidden concerted step with retention of the geometrical configuration of the parent olefin to yield a cyclopropyl radica… Show more

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Cited by 52 publications
(26 citation statements)
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“…The observation of a quartet ground state carbyne is quite unusual, as the previously reported carbyne radicals have doublet ground state . The preference of a doublet ground state for carbyne radicals can be understood from the bonding of the methylidyne HC radical, which has a doublet 2 Π ground state with a quartet state lying 17.1 kcal mol −1 higher in energy .…”
Section: Resultsmentioning
confidence: 80%
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“…The observation of a quartet ground state carbyne is quite unusual, as the previously reported carbyne radicals have doublet ground state . The preference of a doublet ground state for carbyne radicals can be understood from the bonding of the methylidyne HC radical, which has a doublet 2 Π ground state with a quartet state lying 17.1 kcal mol −1 higher in energy .…”
Section: Resultsmentioning
confidence: 80%
“…Previous experimental and theoretical studies indicate that the reactivity patterns of the carbyne radicals in their doublet and quartet spin states are rather different . Such radicals in the doublet state with one unpaired electron and one electron pair on carbon are found to be very reactive toward alkenes and they can even insert into the well‐known inert C−H bonds.…”
Section: Introductionmentioning
confidence: 99%
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“…Theobservation of aquartet ground state carbyne is quite unusual, as the previously reported carbyne radicals have doublet ground state. [2,[9][10][11][12][13][14][15][16] Thep reference of ad oublet ground state for carbyne radicals can be understood from the bonding of the methylidyne HC radical, which has ad oublet 2 P ground state with aq uartet state lying 17.1 kcal mol À1 higher in energy. [31] Theg round state HC radical has an electron configuration of (1s) 2 (2s) 2 (3s) 2 (1p) 1 .…”
Section: Angewandte Chemiementioning
confidence: 99%
“…[10][11][12][13][14][15][16] Such radicals in the doublet state with one unpaired electron and one electron pair on carbon are found to be very reactive toward alkenes and they can even insert into the well-known inert C À Hb onds.Byc ontrast, the quartet state radicals with three unpaired electrons prefer to react with radicals and are prone to H-abstraction reactions.T he experimentally known carbynes predominately have doublet electronic ground states. [2,[9][10][11][12][13][14][15][16] Thep ossibility of tuning the ground state electronic spin from the low-spin doublet to high spin quartet for carbynes has been theoretically discussed and predicted. [17][18][19] Chemical substitutions with greater electropositivity (s-donation) and p-acceptance of the single substituent were predicted to favor the high-spin state.S ome carbynes with quartet ground spin state were predicted.…”
Section: Introductionmentioning
confidence: 99%