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Volumn 125, Issue 14, 2003, Pages 4042-4043

Prospecting for a 5-center 4-electron (C-H-C-H-C)+ bonding array

Author keywords

[No Author keywords available]

Indexed keywords

HYDROCARBON;

EID: 0037427305     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja021394s     Document Type: Article
Times cited : (26)

References (27)
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    • For leading references on the pioneering work of Sorensen and McMurry on acyclic 3-center 2-electron carbocations, see: McMurry, J. E.; Lectka, T. Acc. Chem. Res. 1992, 25, 47-53. For general reviews that also describe cyclic 3-center 2-electron cations, see: Saunders: M.; Jimenez-Vazquez, H. A. Chem. Rev. 1991, 91, 375-397; Grob, C. A. Acc. Chem. Res. 1983, 16, 426-431; Brown, H. C. Acc. Chem. Res. 1983, 16, 432-440.
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  • 2
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    • For leading references on the pioneering work of Sorensen and McMurry on acyclic 3-center 2-electron carbocations, see: McMurry, J. E.; Lectka, T. Acc. Chem. Res. 1992, 25, 47-53. For general reviews that also describe cyclic 3-center 2-electron cations, see: Saunders: M.; Jimenez-Vazquez, H. A. Chem. Rev. 1991, 91, 375-397; Grob, C. A. Acc. Chem. Res. 1983, 16, 426-431; Brown, H. C. Acc. Chem. Res. 1983, 16, 432-440.
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    • Saunders, M.1    Jimenez-Vazquez, H.A.2
  • 3
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    • For leading references on the pioneering work of Sorensen and McMurry on acyclic 3-center 2-electron carbocations, see: McMurry, J. E.; Lectka, T. Acc. Chem. Res. 1992, 25, 47-53. For general reviews that also describe cyclic 3-center 2-electron cations, see: Saunders: M.; Jimenez-Vazquez, H. A. Chem. Rev. 1991, 91, 375-397; Grob, C. A. Acc. Chem. Res. 1983, 16, 426-431; Brown, H. C. Acc. Chem. Res. 1983, 16, 432-440.
    • (1983) Acc. Chem. Res. , vol.16 , pp. 426-431
    • Grob, C.A.1
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    • 0001195988 scopus 로고
    • For leading references on the pioneering work of Sorensen and McMurry on acyclic 3-center 2-electron carbocations, see: McMurry, J. E.; Lectka, T. Acc. Chem. Res. 1992, 25, 47-53. For general reviews that also describe cyclic 3-center 2-electron cations, see: Saunders: M.; Jimenez-Vazquez, H. A. Chem. Rev. 1991, 91, 375-397; Grob, C. A. Acc. Chem. Res. 1983, 16, 426-431; Brown, H. C. Acc. Chem. Res. 1983, 16, 432-440.
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    • Brown, H.C.1
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    • (b) Geometries were optimized without symmetry constraints at the B3LYP/6-31G(d) level (Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652, Becke, A. D. J. Chem. Phys. 1993, 98, 1372-1377, Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1998, 37, 785-789, P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994. 98, 11623-11627). Several recent reports have discussed the use of B3LYP for computing geometries and energetics of 3-center 2-electron cations (Vrcek, I. V.; Vrcek, V.; Siehl, H.-U. J. Phys. Chem. A 2002, 106, 1604-1611 and Farcasiu, D.; Lukinskas, P.; Pamidighantam, S. V. J. Phys. Chem. A 2002, 106, 11672-11675.). These papers suggest that B3LYP tends to underestimate the stability of delocalized structures relative to MP2. but that B3LYP gives comparable results to CCSD.
    • (1993) J. Chem. Phys. , vol.98 , pp. 5648-5652
    • Becke, A.D.1
  • 7
    • 34250817103 scopus 로고
    • (b) Geometries were optimized without symmetry constraints at the B3LYP/6-31G(d) level (Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652, Becke, A. D. J. Chem. Phys. 1993, 98, 1372-1377, Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1998, 37, 785-789, P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994. 98, 11623-11627). Several recent reports have discussed the use of B3LYP for computing geometries and energetics of 3-center 2-electron cations (Vrcek, I. V.; Vrcek, V.; Siehl, H.-U. J. Phys. Chem. A 2002, 106, 1604-1611 and Farcasiu, D.; Lukinskas, P.; Pamidighantam, S. V. J. Phys. Chem. A 2002, 106, 11672-11675.). These papers suggest that B3LYP tends to underestimate the stability of delocalized structures relative to MP2. but that B3LYP gives comparable results to CCSD.
    • (1993) J. Chem. Phys. , vol.98 , pp. 1372-1377
    • Becke, A.D.1
  • 8
    • 0345491105 scopus 로고    scopus 로고
    • (b) Geometries were optimized without symmetry constraints at the B3LYP/6-31G(d) level (Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652, Becke, A. D. J. Chem. Phys. 1993, 98, 1372-1377, Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1998, 37, 785-789, P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994. 98, 11623-11627). Several recent reports have discussed the use of B3LYP for computing geometries and energetics of 3-center 2-electron cations (Vrcek, I. V.; Vrcek, V.; Siehl, H.-U. J. Phys. Chem. A 2002, 106, 1604-1611 and Farcasiu, D.; Lukinskas, P.; Pamidighantam, S. V. J. Phys. Chem. A 2002, 106, 11672-11675.). These papers suggest that B3LYP tends to underestimate the stability of delocalized structures relative to MP2. but that B3LYP gives comparable results to CCSD.
    • (1998) Phys. Rev. B , vol.37 , pp. 785-789
    • Lee, C.1    Yang, W.2    Parr, R.G.3
  • 9
    • 33751157732 scopus 로고
    • (b) Geometries were optimized without symmetry constraints at the B3LYP/6-31G(d) level (Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652, Becke, A. D. J. Chem. Phys. 1993, 98, 1372-1377, Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1998, 37, 785-789, P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994. 98, 11623-11627). Several recent reports have discussed the use of B3LYP for computing geometries and energetics of 3-center 2-electron cations (Vrcek, I. V.; Vrcek, V.; Siehl, H.-U. J. Phys. Chem. A 2002, 106, 1604-1611 and Farcasiu, D.; Lukinskas, P.; Pamidighantam, S. V. J. Phys. Chem. A 2002, 106, 11672-11675.). These papers suggest that B3LYP tends to underestimate the stability of delocalized structures relative to MP2. but that B3LYP gives comparable results to CCSD.
    • (1994) J. Phys. Chem. , vol.98 , pp. 11623-11627
    • Stephens, P.J.1    Devlin, F.J.2    Chabalowski, C.F.3    Frisch, M.J.4
  • 10
    • 0037187139 scopus 로고    scopus 로고
    • (b) Geometries were optimized without symmetry constraints at the B3LYP/6-31G(d) level (Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652, Becke, A. D. J. Chem. Phys. 1993, 98, 1372-1377, Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1998, 37, 785-789, P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994. 98, 11623-11627). Several recent reports have discussed the use of B3LYP for computing geometries and energetics of 3-center 2-electron cations (Vrcek, I. V.; Vrcek, V.; Siehl, H.-U. J. Phys. Chem. A 2002, 106, 1604-1611 and Farcasiu, D.; Lukinskas, P.; Pamidighantam, S. V. J. Phys. Chem. A 2002, 106, 11672-11675.). These papers suggest that B3LYP tends to underestimate the stability of delocalized structures relative to MP2. but that B3LYP gives comparable results to CCSD.
    • (2002) J. Phys. Chem. A , vol.106 , pp. 1604-1611
    • Vrcek, I.V.1    Vrcek, V.2    Siehl, H.-U.3
  • 11
    • 0037191851 scopus 로고    scopus 로고
    • (b) Geometries were optimized without symmetry constraints at the B3LYP/6-31G(d) level (Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652, Becke, A. D. J. Chem. Phys. 1993, 98, 1372-1377, Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1998, 37, 785-789, P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994. 98, 11623-11627). Several recent reports have discussed the use of B3LYP for computing geometries and energetics of 3-center 2-electron cations (Vrcek, I. V.; Vrcek, V.; Siehl, H.-U. J. Phys. Chem. A 2002, 106, 1604-1611 and Farcasiu, D.; Lukinskas, P.; Pamidighantam, S. V. J. Phys. Chem. A 2002, 106, 11672-11675.). These papers suggest that B3LYP tends to underestimate the stability of delocalized structures relative to MP2. but that B3LYP gives comparable results to CCSD.
    • (2002) J. Phys. Chem. A , vol.106 , pp. 11672-11675
    • Farcasiu, D.1    Lukinskas, P.2    Pamidighantam, S.V.3
  • 12
    • 0242528115 scopus 로고    scopus 로고
    • note
    • (c) Structure 8 was characterized as a minimum by frequency calculations at the B3LYP/3-21G level (we are aware of the issues associated with using B3LYP/3-21G calculations to characterize the nature of this stationary point, but all attempts to perform frequency calculations on 8 with the larger 6-31G(d) basis set proved computationally unfeasible: we believe, on the basis of our experience with related systems, that B3LYP/6-31G(d) frequency calculations would also show 8 to be a true minimum).
  • 14
    • 0000134348 scopus 로고    scopus 로고
    • (a) Related architectures have been proposed as supports for σ-allyl cations, but the C - C distances in such systems appear to be too large to allow for direct carbon-carbon interaction. See, for example: Olson, L. P. Org. Lett. 2000, 2, 3059-3062 and Lipkowitz, K. B.; Larter, R. M.; Boyd, D. B. J. Am. Chem. Soc. 1980, 102, 85-92.
    • (2000) Org. Lett. , vol.2 , pp. 3059-3062
    • Olson, L.P.1
  • 15
    • 0002228337 scopus 로고
    • (a) Related architectures have been proposed as supports for σ-allyl cations, but the C - C distances in such systems appear to be too large to allow for direct carbon-carbon interaction. See, for example: Olson, L. P. Org. Lett. 2000, 2, 3059-3062 and Lipkowitz, K. B.; Larter, R. M.; Boyd, D. B. J. Am. Chem. Soc. 1980, 102, 85-92.
    • (1980) J. Am. Chem. Soc. , vol.102 , pp. 85-92
    • Lipkowitz, K.B.1    Larter, R.M.2    Boyd, D.B.3
  • 17
    • 0000567319 scopus 로고    scopus 로고
    • and references therein
    • 24 and its relatives. See Merschrod, E. F.; Hoffmann, R. Chem. Mater. 1999, 11, 341-351 and references therein. We might ponder further extension of 8 towards an infinite one-dimensional polycation.
    • (1999) Chem. Mater. , vol.11 , pp. 341-351
    • Merschrod, E.F.1    Hoffmann, R.2
  • 18
    • 0033579109 scopus 로고    scopus 로고
    • (a) A related 3-center 4-electron O-C-O cation, supported by a monoanthracene framework, also boasts a central trigonal bipyramidal carbon, in this case substituted by four oxygen atoms. See: Akiba, K.; Yamashita, M.; Yamamoto, Y.; Nagase, S. J. Am. Chem. Soc. 1999, 121, 10644-10645.
    • (1999) J. Am. Chem. Soc. , vol.121 , pp. 10644-10645
    • Akiba, K.1    Yamashita, M.2    Yamamoto, Y.3    Nagase, S.4
  • 19
    • 0001433365 scopus 로고
    • (b) Trigonal bipyramidal carbons have also been found in some cases where a carbon atom is surrounded by five metals (such as Li or Au). See, for example: Jemmis, E. D.; Chandrasekhar, J.; Würthwein, E.; Schleyer, P. v. R. J. Am. Chem. Soc. 1982, 104, 4275-4276 and Scherbaum, F.; Grohmann, A.; Muller, G.; Schmidbaur, H. Angew. Chem., Int. Ed. Engl. 1989, 28, 463-465.
    • (1982) J. Am. Chem. Soc. , vol.104 , pp. 4275-4276
    • Jemmis, E.D.1    Chandrasekhar, J.2    Würthwein, E.3    Schleyer, P.V.R.4
  • 20
    • 84990156916 scopus 로고
    • (b) Trigonal bipyramidal carbons have also been found in some cases where a carbon atom is surrounded by five metals (such as Li or Au). See, for example: Jemmis, E. D.; Chandrasekhar, J.; Würthwein, E.; Schleyer, P. v. R. J. Am. Chem. Soc. 1982, 104, 4275-4276 and Scherbaum, F.; Grohmann, A.; Muller, G.; Schmidbaur, H. Angew. Chem., Int. Ed. Engl. 1989, 28, 463-465.
    • (1989) Angew. Chem., Int. Ed. Engl. , vol.28 , pp. 463-465
    • Scherbaum, F.1    Grohmann, A.2    Muller, G.3    Schmidbaur, H.4
  • 21
    • 0242612849 scopus 로고    scopus 로고
    • note
    • 2 units) has subsequently been shown to also boast a 5-center 4-electron array. P. v. R. Schleyer, personal communication, a "holiday gift" to us, 12/13/02.
  • 24
    • 0242444594 scopus 로고
    • Jones, M., Jr., Moss, R. A., Eds.; Wiley: New York; Chapter 4
    • (c) In some cases, using absolute chemical shifts as a measure of local electron density can be a somewhat risky endeavor (See, for example: Bethell, D. In Reactive Intermediates; Jones, M., Jr., Moss, R. A., Eds.; Wiley: New York, 1978; Chapter 4, Vol. 1). but we believe that the risk is minimal in our case due to the fact that we are primarily interested in relative shifts for closely related structures.
    • (1978) Reactive Intermediates , vol.1
    • Bethell, D.1
  • 25
    • 0001607029 scopus 로고
    • For comparison, we compute a chemical shift of +191 ppm for the central carbon of fully relaxed trityl cation (the experimental value is +211 ppm; see: Ray, G. J.; Kurland, R. J.; Colter, A. K. Tetrahedron 1971, 27, 735-752, Abarca, B.; Asensio, G.; Ballesteros, R.; Varea, T. J. Org. Chem. 1991, 56, 3224-3229 and references therein) and a shift of +370 ppm for the carbon in naked methyl cation (all relative to TMS).
    • (1971) Tetrahedron , vol.27 , pp. 735-752
    • Ray, G.J.1    Kurland, R.J.2    Colter, A.K.3
  • 26
    • 0001479961 scopus 로고
    • For comparison, we compute a chemical shift of +191 ppm for the central carbon of fully relaxed trityl cation (the experimental value is +211 ppm; see: Ray, G. J.; Kurland, R. J.; Colter, A. K. Tetrahedron 1971, 27, 735-752, Abarca, B.; Asensio, G.; Ballesteros, R.; Varea, T. J. Org. Chem. 1991, 56, 3224-3229 and references therein) and a shift of +370 ppm for the carbon in naked methyl cation (all relative to TMS).
    • (1991) J. Org. Chem. , vol.56 , pp. 3224-3229
    • Abarca, B.1    Asensio, G.2    Ballesteros, R.3    Varea, T.4
  • 27
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    • Extended Hückel calculations were performed with Greg Landrum's Yet Another Extended Hückel Molecular Orbital Package (YAeHMOP), available through http://sourceforge.net/projects/yaehmop/.


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