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Volumn 72, Issue 1, 2007, Pages 51-61

Kinetic and thermodynamic stability of acenes: Theoretical study of nucleophilic and electrophilic addition

Author keywords

[No Author keywords available]

Indexed keywords

ANTHRACENES; ELECTROPHILES; ELECTROPHILIC ADDITION; EXOTHERMICITY; NUCLEOPHILES; PENTACENE; TRANSITION STATES (TS);

EID: 33846093552     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo061552o     Document Type: Article
Times cited : (31)

References (87)
  • 1
    • 0003913040 scopus 로고
    • Academic Press: London, UK, Vols, and 2
    • (a) Clar, E. Polycyclic Hydrocarbons; Academic Press: London, UK, 1964; Vols. 1 and 2.
    • (1964) Polycyclic Hydrocarbons , vol.1
    • Clar, E.1
  • 14
    • 33846098634 scopus 로고    scopus 로고
    • Very recently heptacene was photogenerated inside of a polymer matrix and characterized by UV spectroscopy. Mondal, R, Shah, B. K, Neckers, D. C. J. Am. Chem. Soc. 2006, 128, 9612
    • Very recently heptacene was photogenerated inside of a polymer matrix and characterized by UV spectroscopy. Mondal, R.; Shah, B. K.; Neckers, D. C. J. Am. Chem. Soc. 2006, 128, 9612.
  • 19
    • 33846038112 scopus 로고    scopus 로고
    • Konovalov, A. I.; Samuilov, Ya, D.; Berdnikov, E. A. Zh. Org. Khim. 1976, 12, 645.
    • (a) Konovalov, A. I.; Samuilov, Ya, D.; Berdnikov, E. A. Zh. Org. Khim. 1976, 12, 645.
  • 38
    • 0004217488 scopus 로고    scopus 로고
    • NIST Standard Reference Database
    • (a) Hunter, E. P.; Lias, S. G. Chemistry WebBook; NIST Standard Reference Database http://webbook.nist.gov/chemistry/.
    • Chemistry WebBook
    • Hunter, E.P.1    Lias, S.G.2
  • 48
    • 32144434172 scopus 로고    scopus 로고
    • However, we note that NICS values cannot be used as a single criterion for aromaticity: see:, and references therein
    • However, we note that NICS values cannot be used as a single criterion for aromaticity: see: Stanger, A. J. Org. Chem. 2006, 71, 883 and references therein.
    • (2006) J. Org. Chem , vol.71 , pp. 883
    • Stanger, A.1
  • 50
    • 33846118705 scopus 로고    scopus 로고
    • Frisch, M. J, Trucks, G. W, Schlegel, H. B, Scuseria, G. E, Robb, M. A, Cheeseman, J. R, Montgomery, J. A, Jr, Vreven, T, Kudin, K. N, Burant, J. C, Millam, J. M, Iyengar, S. S, Tomasi, J, Barone, V, Mennucci, B, Cossi, M, Scalmani, G, Rega, N, Petersson, G. A, Nakatsuji, H, Hada, M, Ehara, M, Toyota, K, Fukuda, R, Hasegawa, J, Ishida, M, Nakajima, T, Honda, Y, Kitao, O, Nakai, H, Klene, M, Li, X, Knox, J. E, Hratchian, H. P, Cross, J. B, Adamo, C, Jaramillo, J, Gomperts, R, Stratmann, R. E, Yazyev, O, Austin, A. J, Cammi, R, Pomelli, C, Ochterski, J. W, Ayala, P. Y, Morokuma, K, Voth, G. A, Salvador, P, Dannenberg, J. J, Zakrzewski, V. G, Dapprich, S, Daniels, A. D, Strain, M. C, Farkas, O, Malick, D. K, Rabuck, A. D, Raghavachari, K, Foresman, J. B, Ortiz, J. V, Cui, Q, Baboul, A. G, Clifford, S, Cioslowski, J, Stefanov, B. B, Liu, G, Liashenko, A, Piskorz, P, Komaromi, I, Martin, R. E, Fox, D. J, Keith, T, Al-Ea
    • Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. E.; Fox, D. J.; Keith, T.; Al-Eaham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Revision C.02; Gaussian, Inc.: Wallingford, CT, 2004.
  • 58
    • 33846042453 scopus 로고    scopus 로고
    • Glendening, E. D.; Badenhoop, J. K.; Reed, A. E.; Carpenter, J. E.; Weinhold, F. NBO 3.1.
    • (a) Glendening, E. D.; Badenhoop, J. K.; Reed, A. E.; Carpenter, J. E.; Weinhold, F. NBO 3.1.
  • 68
    • 33846107323 scopus 로고    scopus 로고
    • 3 gives deuterium exchange. See p 679 in ref 3.
    • 3 gives deuterium exchange. See p 679 in ref 3.
  • 69
    • 33846035655 scopus 로고    scopus 로고
    • Calculated results for addition of HCl and water to acenes in different solvents with use of PCM model are given in the Supporting Information
    • Calculated results for addition of HCl and water to acenes in different solvents with use of PCM model are given in the Supporting Information.
  • 70
    • 33846101970 scopus 로고    scopus 로고
    • These complexes do not necessarily comprise all possible complexes between HCl or water and acenes
    • These complexes do not necessarily comprise all possible complexes between HCl or water and acenes.
  • 71
    • 33846047305 scopus 로고    scopus 로고
    • The spin contamination (S2) of these TSs (S2 of corresponding acenes are given in parantheses)16 are 0.15 (0.26, 0.28 (0.80, 0.37 (1.08, and 0.43 (1.26) respectively for hexacene, heptacene, octacene, and nonacene. Thus, the S2 values for transition states are smaller than those for the corresponding acenes.16 which is due to the partial deformation from planarity in acene backbone that occurs in the transition state, which destabilizes the disjoint biradical structure and generates a preference for the closed shell state
    • 16 which is due to the partial deformation from planarity in acene backbone that occurs in the transition state, which destabilizes the disjoint biradical structure and generates a preference for the closed shell state.
  • 72
    • 33846064592 scopus 로고    scopus 로고
    • α-Cl) distances in the transition states are the following: 1.203 Å (2.742 Å) in 1-HCl-1,4-TS, 1.201 Å (2.872 Å) in 2-HCl-TS, 1.193 Å (3.110 Å) in 3-HCl-TS, 1.189 Å (3.256 Å) in 4-HCl-TS, 1.184 Å (3.463 Å) in 5-HCl-TS, 1.166 Å (3.689 Å) in 6-HCl-TS, 1.155 Å (3.932 Å) in 7-HCl-TS, 1.150 Å (4.055 Å) in 8-HCl-TS, and 1.145 Å (4.184 Å) in 9-HCl-TS. The data for reactions which involve acenes 6-9 are at UB3LYP/6-31G(d).
    • α-Cl) distances in the transition states are the following: 1.203 Å (2.742 Å) in 1-HCl-1,4-TS, 1.201 Å (2.872 Å) in 2-HCl-TS, 1.193 Å (3.110 Å) in 3-HCl-TS, 1.189 Å (3.256 Å) in 4-HCl-TS, 1.184 Å (3.463 Å) in 5-HCl-TS, 1.166 Å (3.689 Å) in 6-HCl-TS, 1.155 Å (3.932 Å) in 7-HCl-TS, 1.150 Å (4.055 Å) in 8-HCl-TS, and 1.145 Å (4.184 Å) in 9-HCl-TS. The data for reactions which involve acenes 6-9 are at UB3LYP/6-31G(d).
  • 73
    • 33846062275 scopus 로고    scopus 로고
    • α⋯Cl) distances at RB3LYP/6-31G(d) are the following: 1.182 Å (3.613 Å) in 6-HCl-TS-R. 1.180 Å (3.815 Å) in 7-HCl-TS-R, 1.178 Å (3.974 Å) in 8-HCl-TS-R, and 1.175 Å (4.168 Å) in 9-HCl-TS-R.
    • α⋯Cl) distances at RB3LYP/6-31G(d) are the following: 1.182 Å (3.613 Å) in 6-HCl-TS-R. 1.180 Å (3.815 Å) in 7-HCl-TS-R, 1.178 Å (3.974 Å) in 8-HCl-TS-R, and 1.175 Å (4.168 Å) in 9-HCl-TS-R.
  • 74
    • 84962420318 scopus 로고    scopus 로고
    • A similar transition state was reported for water addition to silene and its nucleophilic-electrophilic nature was discussed in detail in: Bendikov, M, Quadt, S. R, Rabin, O, Apeloig, Y. Organometallics 2002, 21, 3930
    • A similar transition state was reported for water addition to silene and its nucleophilic-electrophilic nature was discussed in detail in: Bendikov, M.; Quadt, S. R.; Rabin, O.; Apeloig, Y. Organometallics 2002, 21, 3930.
  • 75
    • 33846060618 scopus 로고    scopus 로고
    • The respective Cβ⋯H (Cα⋯ OH) distances are the following: 1.407 Å (1.840 Å) in 1-H 2O-1,4-TS, 1.433 Å (1.864 Å) in 2-H 2O-TS, 1.503 Å (1.869 Å) in 3-H 2O-TS, 1.533 Å (1.868 Å) in 4-H 2O-TS, 1.578 Å (1.862 Å) in 5-H 2O-TS, 1.601 Å (1.858 Å) in 6-H 2O-TS, 1.628 Å (1.855 Å) in 7-H 2O-TS, 1.648 Å (1.847 Å) in 8-H 2O-TS, and 1.666 Å (1.842 Å) in 9-H 2O-TS
    • 2O-TS.
  • 76
    • 33846053477 scopus 로고    scopus 로고
    • At the RB3LYP/6-31G(d) level of theory, the exothermicity of addition reactions continuously increases from benzene to nonacene Tables 4 and 5
    • At the RB3LYP/6-31G(d) level of theory, the exothermicity of addition reactions continuously increases from benzene to nonacene (Tables 4 and 5).
  • 77
    • 33846116973 scopus 로고    scopus 로고
    • Other reactions, such as dimerization or reaction with oxygen, might also prevent isolation of longer acenes
    • Other reactions, such as dimerization or reaction with oxygen, might also prevent isolation of longer acenes.
  • 85
    • 33846085940 scopus 로고    scopus 로고
    • See ref 11
    • (h) See ref 11.
  • 86
    • 33846084136 scopus 로고    scopus 로고
    • 3 were used for Figure 11 and eq 1 as the best available σ values for molecules in Scheme 2.
    • 3 were used for Figure 11 and eq 1 as the best available σ values for molecules in Scheme 2.
  • 87
    • 3042811341 scopus 로고    scopus 로고
    • It is also known that pentacene substituted by electron-withdrawing groups is an n-type organic semiconductor. Sakamoto, Y.; Suzuki, T.; Kobayashi, M.; Gao, Y.; Fukai, Y.; Inoue, Y.; Sato, F.; Tokito, S. J. Am. Chem. Soc. 2004, 126, 8138.
    • It is also known that pentacene substituted by electron-withdrawing groups is an n-type organic semiconductor. Sakamoto, Y.; Suzuki, T.; Kobayashi, M.; Gao, Y.; Fukai, Y.; Inoue, Y.; Sato, F.; Tokito, S. J. Am. Chem. Soc. 2004, 126, 8138.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.