Subscribe to RSS
DOI: 10.1055/s-2003-39284
Angular Group Induced Bond Alternation (AGIBA). A New Face of Substituent Effect Detected in Molecular Geometry
Publication History
Publication Date:
20 May 2003 (online)
Abstract
Angular Group Induced Bond Alternation is a new face of a substituent effect well documented by careful analysis of molecular geometry. The angular groups attached to monocyclic 6-π-electron systems cause substantial changes to π-electron distribution in the ring. Different patterns are found for X-Y and X=Y types of groups. The overall effect is due to the rehybridization effect, the through space π-electron interactions between a group and the ring, possibly also by other subtle effects, eg. the negative hyperconjugation. The effect is strongly conformational dependent. While the AGIBA is energetically weak, it is structurally strong enough that other interactions in monocyclic systems, eg. through - resonance type interactions do not reduce it. In polycyclic benzenoid hydrocarbons AGIBA works only locally while in non-cyclic π-electron systems the effect does not work at all.
Key words
AGIBA - substituent effects - benzene derivatives - π-electron systems
- 1
Hammett LP. Chem. Rev. 1935, 35: 1 - 2
Hammett LP. J. Am. Chem. Soc. 1937, 59: 96 - 3
Jaffe HH. Chem. Rev. 1953, 53: 191 - 4
Exner O. In Advances in Linear Free Energy RelationshipsChapman NB.Shorter J. Plenum Press; London: 1972. - 5
Johnson CD. The Hammett Equation Cambridge University Press; Cambridge: 1973. - 6
Shorter J. In Similarity Models in Chemistry Biochemistry and Related FieldsZalewski RI.Krygowski TM.Shorter J. Elsevier; Amsterdam: 1991. - 7
Allen FH.Davies JE.Galloy JJ.Johnson O.Kennard O.McRae EM.Mitchell GF.Smith JM.Watson DG. J. Chem. Inf. Comput. Sci. 1991, 31: 187 ; Note that Cambridge Structural Database archives much more than 200,000 crystal structures and molecular geometries of organic compounds - 8
Domenicano A.Vaciago A.Coulson CA. Acta Crystallogr., Sect. B 1975, 31: 221 - 9
Domenicano A.Vaciago A.Coulson CA. Acta Crystallogr., Sect. B 1975, 31: 1630 - 10
Domenicano A.Mazzeo P.Vaciago A. Tetrahedron Lett. 1976, 1029 - 11
Walsh AD. Discuss. Faraday Soc. 1947, 2: 18 - 12
Bent HA. Chem. Rev. 1961, 61: 275 - 13
Gillespie RJ. Molecular Geometry Van Nostrand-Reinhold; London: 1972. - 14
Krygowski TM. J. Chem. Res., Synop. 1984, 238 - 15
Maurin J.Krygowski TM. J. Mol. Struct. 1988, 172: 413 - 16
Krygowski TM. J. Chem. Res., Synop. 1987, 120 - 17
Bock CW.Trachtmann M.George P. J. Mol. Struct. 1985, 122: 155 - 18
Krygowski TM.Häfelinger G.Schule J. Z. Naturforsch. B: Chem. Sci. 1985, 41: 895 - 19
Häfelinger G.Regelmann CU.Krygowski TM.WoŸniak K. J. Comput. Chem. 1988, 10: 329 -
20a
Shaik SS.Hiberty PC. J. Am. Chem. Soc. 1985, 107: 3089 -
20b
Hiberty PC.Shaik SS.Ohanessian G.Lefour JM. J. Org. Chem. 1986, 51: 3908 -
20c
Hiberty PC. Top. Curr. Chem. 1990, 153: 27 - 21
Jug K.Köster A. J. Am. Chem. Soc. 1990, 112: 6772 - 22
Jug K.Hiberty P.Shaik S. Chem. Rev. 2001, 101: 1477 ; and references therein - 23
Jeffrey GA.Ruble JR.McMullan RK.Pople JA. Proc. R. Soc. London 1987, A414: 47 - 24
Lipkowitz KB.Peterson MA. J. Comput. Chem. 1993, 14: 121 - 25
Cyrański MK.Krygowski TM. Tetrahedron 1999, 55: 6209 - 26
Schleyer PvR.Jiao H. Pure Appl. Chem. 1996, 68: 209 - 27
Krygowski TM.Anulewicz R.Jarmua A.Bąk T.Rasaa D.Howard ST. Tetrahedron 1994, 50: 13155 - 28
Krygowski TM.Anulewicz R.Kruszewski J. Acta Crystallogr., Sect. B 1983, 39: 732 - 29
Karolak-Wojciechowska J. Acta Crystallogr., Sect. B 1987, 43: 574 - 30
Krygowski TM. In Structure and ReactivityLiebman JF.Greenberg A. VCH; Weinheim: 1988. Chap. 6. p.231 - 31
Krygowski TM. Prog. Phys. Org. Chem. 1991, 17: 239 - 32
Krygowski TM.Cyrański MK. Molecular Geometry as a Source of Chemical Information of π-Electron Compounds In Theoretical and Computational Chemistry Vol. 5: Elsevier; Amsterdam: 1998. p.153 - 33
Randić M. Tetrahedron 1977, 33: 1905 - 34
Hammett LP. Physical Organic Chemistry McGraw-Hill Inc.; New York: 1970. - 35
Krygowski TM.Turowska-Tyrk I. Collect. Czech. Chem. Commun. 1990, 55: 165 - 36
Cyrański M.Krygowski TM. Pol. J. Chem. 1996, 69: 1088 - 37
Jarmua A.Leś A.Rode W. Bioorg. Chem. 2000, 28: 156 - 38
Rode W.Leś A. Acta Biochem. Pol. 1996, 43: 133 - 39
Dzik JM.Bretner M.Kulikowski T.Goos B.Jarmua A.Poznański J.Rode W.Shugar D. Biochim. Biophys. Acta 1996, 1382: 277 - 40
Bird CW. Tetrahedron 1997, 53: 13111 - 41
Bird CW. Tetrahedron 1997, 53: 17195 - 42
Bird CW. Tetrahedron 1998, 54: 5641 - 43
Howard ST.Krygowski TM.Gówka ML. Tetrahedron 1996, 52: 11379 - 44
Krygowski TM.Howard ST.Martynowski D.Gówka ML. J. Phys. Org. Chem. 1997, 10: 125 - 45
Krygowski TM.Pindelska E.Cyrański MK.Nowacki J. Int. Electr. J. Mol. Des. 2002, 1: 593 - 46
Krygowski TM.Cyrański M.Wisiorowski M. Pol. J. Chem. 1996, 71: 1351 - 47
Krygowski TM.Anulewicz R.Hiberty PC. J. Org. Chem. 1996, 61: 8533 - 48
Boese R.Polk M.Blaser D. Angew. Chem., Int. Ed. Engl. 1987, 28: 245 - 49
Maulitz AH.Stellberg P.Boese R. J. Mol. Struct. 1995, 338: 131 - 50
Boyd RJ.Choi SC.Hale CC. Chem. Phys. Lett. 1984, 112: 126 - 51
Haddon RC. Pure Appl. Chem. 1982, 45: 1129 - 52
Jemmis ED.Kiran B. Inorg. Chem. 1998, 37: 2110 - 53
Schleyer PvR.Jiao H.Hommes NJRvE.Malkin VG.Malkina OL. J. Am. Chem. Soc. 1997, 119: 12669 - 54
Krygowski TM.Cyrański MK. Chem. Rev. 2001, 101: 1385 - 55
Stanger A.Vollhardt KPC. J. Org. Chem. 1988, 53: 4889 - 56
Stanger A. J. Am. Chem. Soc. 1991, 113: 8277 -
57a
Maksić ZB.Eckert-Maksić M.Hodoscek M.Koch W.Kovacek D. In Molecules in Natural Science and MedicineMaksiæ ZB.Eckert-Maksić M. Ellis Horwood; Chichester: 1991. p.334 -
57b
Koch W.Eckert-Maksić M.Maksić ZB. Int. J. Quant. Chem. 1993, 48: 319 -
58a
Krygowski TM.Pindelska E.Cyrański MK.Häfelinger G. Chem. Phys. Lett. 2002, 359: 158 -
58b
Fowler PW.Havenith RWA.Jenneskens LW.Soncini A.Steiner E. Angew. Chem. Int. Ed. 2002, 41: 1558 - 59 See also:
Klärner F.-G. Angew. Chem. Int. Ed. 2001, 40: 3977 - 60
Stanger A. J. Am. Chem. Soc. 1998, 120: 12034 - 61
Schleyer PvR.Kos A. Tetrahedron 1983, 39: 1141 - 62
Krygowski TM.Wisiorowski M.Howard ST.Stolarczyk LZ. Tetrahedron 1997, 53: 13027 - 63
Howard ST.Krygowski TM.Ciesielski A.Wisiorowski M. Tetrahedron 1998, 54: 3533 - 64
Bader RFW. Atoms in Molecules. A Quantum Theory Oxford University Press; Oxford: 1990. - 65
Minkin VI.Glukhovtsev MN.Simkin BY. Aromaticity and Antiaromaticity - Electronic and Structural Aspects Wiley; New York: 1994. - 66
Krygowski TM.Cyrański MK.Czarnocki Z.Häfelinger G.Katritzky AR. Tetrahedron 2000, 56: 1783 - 67
Krygowski TM.Pindelska E.Anulewicz-Ostrowska R.Grabowski SJ.Dubis A. J. Phys. Org. Chem. 2001, 14: 349 - 68
Taft RW.Lewis IC. J. Am. Chem. Soc. 1958, 80: 2436 - 69
Stūpień BT.Cyrański MK.Krygowski TM. Chem. Phys. Lett. 2001, 350: 537 - 70
Krygowski TM.Piūtka E.Anulewicz R.Cyrański MK.Nowacki J. Tetrahedron 1998, 54: 12289 - 71
Pindelska E.Krygowski TM.Anulewicz-Ostrowska R.Cyrański MK.Nowacki J. J. Phys. Org. Chem. 2001, 14: 764 - 72
Krygowski TM.Pindelska E.Anulewicz-Ostrowska R.Nowacki J. Pol. J. Chem. 2002, 76: 1249 - 73
Krygowski TM.Pindelska E. Pol. J. Chem. 2002, 76: 325 - 74
Wilson CC.Shankland N.Florence AJ. J. Chem. Soc., Faraday Trans. 1996, 92: 5051 - 75
Krygowski TM.Pindelska E.Cyrański MK.Grabowski SJ. Tetrahedron 2000, 56: 8715 - 76
Krygowski TM.Cyrański M.Ciesielski A.Świrska B.Leszczyński P. J. Chem. Inf. Comput. Sci. 1996, 36: 1135 - 77
Cyrański M.Krygowski TM. J. Chem. Inf. Comput. Sci. 1996, 36: 1142 - 78
Halton B. In Chemistry of Cyclopropenyl GroupRappoport Z. Vol. 2: Wiley; New York: 1995. Chap. 12. p.707 - 79
Frank NL.Siegel J. Adv. Theoretically Interesting Molecules 1995, 3: 209 - 80
Maksić ZB.Eckert-Maksić M.Mo O.Yanez M. In Pauling’s Legacy - Modern Modelling of the Chemical Bond Vol. 6:Maksić ZB.Orville-Thomas WJ.Politzer P.Maksić ZB. Elsevier; Amsterdam: 1999. p.47 - 81
Boese R.Bläser D.Billups E.Haley MM.Maulitz AH.Mohler DL.Vollhardt KPC. Angew. Chem., Int. Ed. Engl. 1994, 33: 313 - 82
Diercks R.Vollhardt KPC. J. Am. Chem. Soc. 1986, 108: 3150 - 83
Frank NL.Baldridge KM.Siegel J. J. Am. Chem. Soc. 1995, 117: 2102