메뉴 건너뛰기




Volumn 89, Issue 2, 2011, Pages 235-240

A computational study of the fluctional behaviour of group 14 substituted ortho -semiquinone radicals

Author keywords

Density functional theory; Group migration; Group coupled electron transfer; Kinetics; Semiquinone radicals

Indexed keywords

ARRHENIUS PARAMETERS; COMPUTATIONAL STUDIES; EXPERIMENTAL DATA; EXPERIMENTAL VALUES; GROUP MIGRATION; GROUP-COUPLED ELECTRON TRANSFER; SEMIQUINONE RADICALS;

EID: 79951503450     PISSN: 00084042     EISSN: None     Source Type: Journal    
DOI: 10.1139/V10-082     Document Type: Article
Times cited : (1)

References (36)
  • 3
    • 79951474473 scopus 로고    scopus 로고
    • 3PbOO •. Calculated values are given in ref. 1.
    • 3PbOO •. Calculated values are given in ref. 1.
  • 4
    • 0642273576 scopus 로고
    • For reviews of these and analogous reactions, see 10.1070/ RC1978v047n06ABEH002238
    • For reviews of these and analogous reactions, see: (a) Bubnov, N. N.; Solodovnikov, S. P.; Prokof'ev, A. I.; Kabachnik, M. I. Russ. Chem. Rev. 1978, 47 (6), 549. 10.1070/RC1978v047n06ABEH002238;
    • (1978) Russ. Chem. Rev. , vol.47 , Issue.6 , pp. 549
    • Bubnov, N.N.1    Solodovnikov, S.P.2    Prokof'Ev, A.I.3    Kabachnik, M.I.4
  • 6
    • 0040770210 scopus 로고
    • For a review of solvent viscosity effects on the rates of these fast uni molecular reactions, see 10.1070/RC1993v062n06ABEH000030
    • For a review of solvent viscosity effects on the rates of these fast uni molecular reactions, see: (c) Rakhimov, R. R.; Prokof'ev, A. I.; Lebedev, Ya. S. Russ. Chem. Rev. 1993, 62 (6), 509. 10.1070/RC1993v062n06ABEH000030
    • (1993) Russ. Chem. Rev. , vol.62 , Issue.6 , pp. 509
    • Rakhimov, R.R.1    Prokof'Ev, A.I.2    Lebedev Ya., S.3
  • 10
    • 79951503055 scopus 로고    scopus 로고
    • Similar results and conclusions have been reported for adducts of tri-substituted group 14 radicals with other 1,2-dicarbonyl compounds. 9
    • Similar results and conclusions have been reported for adducts of tri-substituted group 14 radicals with other 1,2-dicarbonyl compounds. 9
  • 11
    • 0011782110 scopus 로고
    • 10.1016/0009-2614(77)80326-6
    • See for example: (a) Alberti, A.; Hudson, A. Chem. Phys. Lett. 1977, 48 (2), 331. 10.1016/0009-2614(77)80326-6;
    • (1977) Chem. Phys. Lett. , vol.48 , Issue.2 , pp. 331
    • Alberti, A.1    Hudson, A.2
  • 14
  • 17
    • 79951504795 scopus 로고    scopus 로고
    • H2 process. 11 Instead, it involves a nucleophilic attack of an oxygen lone pair on the empty boron p orbital. The unpaired electron on the oxygen is not directly involved, but the boron-ligand bond aligned with the SOMO cleaves and the ligand leaves promptly. The mechanism was described as a nucleophilic homolytic substitution at boron
    • H2 process. 11 Instead, it involves a nucleophilic attack of an oxygen lone pair on the empty boron p orbital. The unpaired electron on the oxygen is not directly involved, but the boron-ligand bond aligned with the SOMO cleaves and the ligand leaves promptly. The mechanism was described as a nucleophilic homolytic substitution at boron.
  • 18
    • 53849097033 scopus 로고    scopus 로고
    • 10.1002/ejoc.200800187
    • Carra, C.; Scaiano, J. C. Eur. J. Org. Chem. 2008, 2008 (26), 4454. 10.1002/ejoc.200800187
    • (2008) Eur. J. Org. Chem. , vol.2008 , Issue.26 , pp. 4454
    • Carra, C.1    Scaiano, J.C.2
  • 20
    • 79951505427 scopus 로고    scopus 로고
    • Calculations were performed using B3 14 LYP 15 /6-311+G(d,p) as implemented in ref. 16. For radicals containing Sn, we used the averaged relativistic effective potentials of LaJohn et al. 17 with the accompanying basis set, which was used uncontracted.
    • Calculations were performed using B3 14 LYP 15 /6-311+G(d,p) as implemented in ref. 16. For radicals containing Sn, we used the averaged relativistic effective potentials of LaJohn et al. 17 with the accompanying basis set, which was used uncontracted.
  • 21
    • 0000189651 scopus 로고
    • 10.1063/1.464913
    • Becke, A. D. J. Chem. Phys. 1993, 98, 5648. 10.1063/1.464913
    • (1993) J. Chem. Phys. , vol.98 , pp. 5648
    • Becke, A.D.1
  • 25
    • 79951506405 scopus 로고    scopus 로고
    • It has been reported that "solvents capable of forming hydrogen bonds" retard the rate of reaction 2 for G = H. 4a This is to be expected because phenols containing intramolecular H bonds are capable of forming bifurcated intra/intermolecular H bonds, 19 which reduces the rates of H-atom abstraction 20 just as intermolecular H bonding reduces the rates of abstraction from simple phenols. 21 Fortunately, the experiments in question 4a were done in heptane, which is neither an H-bond donor nor acceptor, so the kinetic measurements should be directly comparable with the computed dynamics.
    • It has been reported that "solvents capable of forming hydrogen bonds" retard the rate of reaction 2 for G = H. 4a This is to be expected because phenols containing intramolecular H bonds are capable of forming bifurcated intra/intermolecular H bonds, 19 which reduces the rates of H-atom abstraction 20 just as intermolecular H bonding reduces the rates of abstraction from simple phenols. 21 Fortunately, the experiments in question 4a were done in heptane, which is neither an H-bond donor nor acceptor, so the kinetic measurements should be directly comparable with the computed dynamics.
  • 30
    • 0003637193 scopus 로고
    • 10.1021/ar00139a004
    • For a summary, see: Wilson, E. B.; Smith, Z. Acc. Chem. Res. 1987, 20 (7), 257. 10.1021/ar00139a004
    • (1987) Acc. Chem. Res. , vol.20 , Issue.7 , pp. 257
    • Wilson, E.B.1    Smith, Z.2
  • 31
    • 36149014576 scopus 로고
    • 10.1103/PhysRev.35.1303
    • Eckart, C. Phys. Rev. 1930, 35, 1303. 10.1103/PhysRev.35.1303
    • (1930) Phys. Rev. , vol.35 , pp. 1303
    • Eckart, C.1
  • 32
    • 0037130656 scopus 로고    scopus 로고
    • Proton-coupled electron transfer versus hydrogen atom transfer in benzyl/toluene, methoxyl/methanol, and phenoxyl/phenol self-exchange reactions
    • DOI 10.1021/ja012732c
    • Mayer, J. M.; Hrovat, D. A.; Thomas, J. L.; Borden, W. T. J. Am. Chem. Soc. 2002, 124 (37), 11142. 10.1021/ja012732c 12224962 (Pubitemid 35025673)
    • (2002) Journal of the American Chemical Society , vol.124 , Issue.37 , pp. 11142-11147
    • Mayer, J.M.1    Hrovat, D.A.2    Thomas, J.L.3    Borden, W.T.4
  • 33
    • 18644375115 scopus 로고    scopus 로고
    • A theoretical study of the iminoxyl/oxime self-exchange reaction. A five-center, cyclic proton-coupled electron transfer
    • DOI 10.1021/ja0500409
    • DiLabio, G. A.; Ingold, K. U. J. Am. Chem. Soc. 2005, 127 (18), 6693. 10.1021/ja0500409 15869291 (Pubitemid 40664176)
    • (2005) Journal of the American Chemical Society , vol.127 , Issue.18 , pp. 6693-6699
    • DiLabio, G.A.1    Ingold, K.U.2
  • 34
    • 34249088888 scopus 로고    scopus 로고
    • Lone pair- and interactions play an important role in proton-coupled electron transfer reactions
    • DOI 10.1021/ja068090g
    • DiLabio, G. A.; Johnson, E. R. J. Am. Chem. Soc. 2007, 129 (19), 6199. 10.1021/ja068090g 17444643 (Pubitemid 46786810)
    • (2007) Journal of the American Chemical Society , vol.129 , Issue.19 , pp. 6199-6203
    • DiLabio, G.A.1    Johnson, E.R.2
  • 35
    • 79951491540 scopus 로고    scopus 로고
    • This particular reaction could be referred to as a stannylium 29 coupled electron transfer
    • This particular reaction could be referred to as a stannylium 29 coupled electron transfer.
  • 36
    • 79951473856 scopus 로고    scopus 로고
    • Stable stannylium cations in condensed phases
    • Davies, A. G., Gielen, M., Pannell, K. H., Kiekink, E. R. T., Eds.; Wiley: Chichester, UK
    • Lambert, J. B. "Stable stannylium cations in condensed phases". In Tin Chemistry, Fundamentals, Frontiers, and Applications; Davies, A. G., Gielen, M., Pannell, K. H., Kiekink, E. R. T., Eds.; Wiley: Chichester, UK, 2009; pp 152-159.
    • (2009) Tin Chemistry, Fundamentals, Frontiers, and Applications , pp. 152-159
    • Lambert, J.B.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.