Factors influencing aromaticity: PCA studies of monosubstituted derivatives of pentafulvene, benzene and heptafulvene

Current Organic Chemistry

Volumn 16, Issue 16, 2012, Pages 1920-1933

  Cysewski, Piotr ^a,b   Jeliński, Tomasz ^a   Krygowski, Tadeusz Marek ^c   Oziminski, Wojciech P ^d  

^a NICOLAUS COPERNICUS UNIVERSITY   (Poland)

^b UNIVERSITY OF TECHNOLOGY AND LIFE SCIENCES   (Poland)

^c UNIVERSITY OF WARSAW   (Poland)

^d NATIONAL MEDICINES INSTITUTE   (Poland)

Author keywords

Aromaticity; Benzene Analogues; Heptafulvene; P electron Delocalization; Pentafulvene; Principal Component Analysis; Solvent Effect; Substituent Effect

Indexed keywords

AROMATIZATION; LAPLACE TRANSFORMS; PRINCIPAL COMPONENT ANALYSIS; QUANTUM CHEMISTRY; SOLVENTS;

AROMATICITIES; BENZENE ANALOG; ELECTRON DELOCALIZATION; HEPTAFULVENE; P-ELECTRON DELOCALIZATION; PENTAFULVENE; PENTAFULVENES; PRINCIPAL-COMPONENT ANALYSIS; SOLVENT EFFECTS; SUBSTITUENT EFFECT;

BENZENE;

EID: 84864540114     PISSN: 13852728     EISSN: None     Source Type: Journal    
DOI: 10.2174/138527212802651205     Document Type: Article

References (104)

1. Bergmann, E.D.; Pullman, B. In: Aromaticity, Pseudo-aromaticity, Antiaromaticity, Proceedings of an International Symposium, Jerusalem, Israel, March 31-April 3,1970; Israel Academy of Science and Humanities: Jerusalem, Israel, 1971.
2. Minkin, V.I.; Glukhovtsev, M.N.; Simkin, B. Ya. Aromaticity and Antiaromaticity:Electronic and Structural Aspects, J. Wiley & Sons: New York,1994.
3. Stanger, A. What is. aromaticity: a critique of the concept of aromaticity-can it really be defined? Chem. Commun., 2009, 15, 1939.
4. Elvidge, J.A.; Jackman, L.M. Studies of aromaticity by nuclear magneticresonance spectroscopy. Part I. 2-Pyridones and related systems. J. Chem. Soc., 1961, 859.
5. Sondheimer, F. Recent advances in the chemistry of large-ring conjugatedsystems. Pure Appl. Chem., 1963, 7, 363.
6. Dewar, M.J.S. A molecular orbital theory of organic chemistry-VIII: aromaticityand electrocyclic reactions. Tetrahedron Suppl., 1966, 8, 75.
7. Krygowski, T.M.; Cyrašski, M.K.; Czarnocki, Z.; Hafelinger, G.; KatritzkyA.R. Aromaticity: a Theoretical Concept of Immense Practical Importance, Tetrahedron, 2000, 56, 1783.
8. Krygowski, T.M.; Cyrašski, M. Structural Aspects of Aromaticity. Chem. Rev., 2001, 101, 1385.
9. Chen, Z.; Wannere, C.S.; Corminboeuf, C.; Puchta R.; Schleyer, P.v.R. Nucleus-Independent Chemical Shifts (NICS) as an Aromaticity Criterion. Chem. Rev., 2005, 105, 3842.
10. Jug, K.; Koester, A. Aromaticity as a multi-dimensional phenomenon. J. Phys. Org. Chem., 1991, 4, 163.
11. Krygowski, T.M.; Ciesielski, A.; Bird, C.W.; Kotschy, A. Aromatic Characterof the Benzene Ring Present in Various Topological Environments inBenzenoid Hydrocarbons. Nonequivalence of Indices of Aromaticity. J. Chem. Inf. Comput. Sci., 1995, 35, 203.
12. Katritzky, A.R.; Karelson, M.; Sild, S.; Krygowski, T.M.; Jug, K. Aromaticityas a Quantitative Concept. 7. Aromaticity Reaffirmed as a MultidimensionalCharacteristic. J. Org. Chem., 1998, 63, 5228.
13. Cyrašski, M.K.; Krygowski, T.M.; Katritzky, A.R.; Schleyer, P.v.R. ToWhat Extent Can Aromaticity Be Defined Uniquely? βJ. Org. Chem., 2002,67, 1333.
14. Poater, J.; Fradera, X.; Duran, M.; Sola, M. The Delocalization Index as anElectronic Aromaticity Criterion: Application to a Series of Planar PolycyclicAromatic Hydrocarbons. Chem. Eur. J., 2003, 9, 400.
15. Poater, J.; Fradera, X.; Duran, M.; Sola, M. An Insight into the Local Aromaticitiesof Polycyclic Aromatic Hydrocarbons and Fullerenes. Chem. Eur.J., 2003, 9, 1113.
16. Matito, E.; Duran, M.; Solá, M. The aromatic fluctuation index (FLU): Anew aromaticity index based on electron delocalization. J. Chem. Phys.,2005, 125, 59901.
17. Palusiak, M.; Krygowski, T.M. Application of AIM Parameters at RingCritical Points for Estimation of π-Electron Delocalization in Six-MemberedAromatic and Quasi-Aromatic Rings. Chem. Eur. J., 2007, 13, 7996.
18. Katritzky, A.R.; Barczynski, P.; Musumarra, G.; Pisano, D.; Szafran, M. Aromaticity as a Quantitative Concept. 1. A Statistical Demonstration of theOrthogonality of "Classical" and "Magnetic" Aromaticity in Five-and Six-Membered Heterocycles. J. Am. Chem. Soc., 1989, 111, 7.
19. Sadlej-Sosnowska, N.; Mutual relationships between magnetic aromaticityindices of heterocyclic compounds, J Phys. Org. Chem., 2004, 17, 303.
20. Alonso, M.; Herradón, B.; Substituent effects on the aromaticity of carbocyclicfive-membered rings, Phys. Chem. Chem. Phys., 2010, 12, 1305.
21. Alonso, M.; Herradón, B.; Neural networks as a tool to classify compoundsaccording to aromaticity criteria, Chem. Eur. J., 2007, 13, 3913.
22. Alonso, M.; Herradón, B.; A universal scale of aromaticity for π-organiccompounds, J. Comput. Chem., 2009, 31, 917.
23. Feixas, F.; Matito E.; Poater, J.; Sola, M. Aromaticity of Distorted BenzeneRings:β Exploring the Validity of Different Indicators of Aromaticity. J. Phys. Chem. A, 2007, 111, 4513.
24. Bultinck, P. Critical analysis of the local aromaticity concept in polyaromatichydrocarbons. Faraday. Discuss., 2007, 135, 347.
25. Fias, S.; van Damme S.; Bultinck, P. J. Multidimensionality of delocalizationindices and nucleus independent chemical shifts in polycyclic aromatic hydrocarbon.J. Comp. Chem., 2008, 29, 358.
26. Subramanian, G.; Schleyer P.V.R.; Jiao, H. Are the Most Stable Fused Heterobicyclesthe Most Aromatic? Angew. Chem. Int. Ed. Engl., 1995, 35,2638.
27. Pauling, L.; Wheland, G.W. The Nature of the Chemical Bond. V. TheQuantum-Mechanical Calculation of the Resonance Energy of Benzene andNaphthalene and the Hydrocarbon Free Radicals. Chem. Phys., 1933, 1, 362.
28. Kistiakovski, G.B.; Ruhoff, J.R.; Smith, H.A.; Vaughan, W. E. Heats ofOrganic Reactions. IV. Hydrogenation of Some Dienes and of Benzene. J. Am. Chem. Soc., 1936, 58, 146.
29. Cyrašski, M.K. Energetic Aspects of Cyclic Pi-Electron Delocalization:βEvaluation of the Methods of Estimating Aromatic Stabilization Energies. Chem. Rev., 2005, 105, 3773.
30. Wodrich, M.D.; Wannere C.S.; Mo Y.; Jarowski, P.D.; Houk K.N.; SchleyerP.v.R. The Concept of Protobranching and Its Many Paradigm Shifting Implicationsfor Energy Evaluations. Chem. Eur. J., 2007, 13, 7731.
31. Mo, Y.; Schleyer, P. v. R.; An energetic measure of aromaticity and antiaromaticitybased on the Pauling-Wheland resonance energies. Chem. Eur. J.,2006, 12, 2009.
32. Fernández, I.; Frenking, G.; Aromaticity in Metallabenzenes. Chem. Eur. J.,2007, 13, 5873.
33. Julg, A.; François, P. Recherches sur la géométrie de quelques hydrocarburesnon-alternants: son influence sur les énergies de transition, une nouvelledéfinition de l'aromaticité. Theor. Chim. Acta, 1967, 8, 249.
34. Kruszewski, J.; Krygowski, T.M. Definition of aromaticity basing on theharmonic oscillator model. Tetrahedron Lett., 1972, 13, 3839.
35. Kruszewski, J.; Krygowski, T.M. In: Aromaticity of Aza-analogues of BenzenoiodHydrocarbons, Proceedings of the Symposium "Synthesis, Structureand Properties of Heterocyclic compounds", Poznan, 1972.
36. Krygowski, T.M. Crystallographic Studies of Inter-and IntramolecularInteractions Reflected in Aromatic Character of α-Electron Systems. J. Chem. Inf: Comput. Sci., 1993, 33, 70.
37. Bird, C.W. A new aromaticity index and its application to five-memberedring heterocycles. Tetrahedron, 1985, 41, 1409.
38. Gordy, W.J. Dependence of Bond Order and of Bond Energy Upon BondLength. J. Chem. Phys., 1947, 14, 305.
39. Pacault, A.; Hoarau, J.; Marchand, A. Aspects Récents DU Diamagnétisme. Adv. in Chem. Phys., 1961, 3, 171.
40. Flygare, W.H. Magnetic interactions in molecules and an analysis of molecularelectronic charge distribution from magnetic parameters. Chem. Rev.,1974, 74, 653.
41. Dauben, H.J.; Wilson J.D.; Laity, J.L., Diamagnetic susceptibility exaltationas a criterion of aromaticity. J. Am. Chem. Soc., 1968, 90, 811.
42. Lazzaretti, P. Ring currents. Prog. Nucl. Magn. Reson. Spectrosc., 2000, 36,1.
43. Lazzaretti P. Assessment of aromaticity via molecular response properties. PCCP, 2004, 6, 217.
44. Steiner, E.; Fowler P.W. Four-and two-electron rules for diatropic andparatropic ring currents in monocyclic systems. J. Chem. Soc. Chem. Comm., 2001, 2220.
45. Schleyer, P.v. R; Maerker, C.; Dransfeld, A.; Jiao, H.; van Eikema Hommes, N.J.R. Nucleus-Independent Chemical Shifts: A Simple and Efficient AromaticityProbe. J. Am. Chem. Soc., 1996, 118, 6317.
46. Ciesielski, A.; Krygowski, T.M.; Cyrański, M.K.; Dobrowolski M.A.;Aihara J. Graph-topological approach to magnetic properties of benzenoidhydrocarbons. Phys. Chem. Chem. Phys., 2009, 11, 11447.
47. Krygowski, T.M.; Anulewicz, R.; Pniewska, B.; Milart, P.; Bock, Ch. W.;Sawada, M.; Takai, Y.; Hanafusa, T. Crystal and molecular structure of thelithium p-nitrosophenolate dihydrate dimer: an example of a strong dependenceof the p-electron cooperative substituent effect on the hydrogenbondingnetwork in the crystal lattice. J. Mol. Struct., 1994, 324, 251.
48. Krygowski, T.M.; Kalinowski, M.K.; Turowska-Tyrk, I.; Hiberty, P.C.;Milart, P.; Silvestro, A.; Topsom, R.D.; Daehne, S. Crystallographic studiesof intra-and intermolecular interactions. Part 4. A comparative study of theeffect of through-resonance on the geometry of p-nitro-and pnitrosophenolateanions. Struct. Chem., 1991, 2, 71.
49. Krygowski, T.M.; Szatyšowicz, H.; Zachara J.E. Molecular Geometry as aSource of Chemical Information. 5. Substituent Effect on Proton Transfer inPara-Substituted Phenol Complexes with Fluoride a B3LYP/6-311+G**Study. J. Chem. Inf. Mod., 2005, 45, 652.
50. Krygowski, T.M.; Ste{ogonek}pień, B.T. Sigma-and Pi-Electron Delocalization:-Focus on Substituent Effects. Chem. Rev., 2005, 105, 3482.
51. Sobczyk, L.; Grabowski, S.J.; Krygowski, T.M. Interrelation between HBondand Pi-Electron Delocalization. Chem. Rev., 2005, 105, 3513.
52. Raczynska, E.D.; Kosinska, W.; Osmialowski, B.; Gawinecki, R. TautomericEquilibria in Relation to Pi-Electron Delocalization. Chem. Rev., 2005, 105,3561.
53. Miertu, S. Scrocco, E. and Tomasi, J.; Electrostatic Interaction of a Solutewith a Continuum. A Direct Utilization of ab initio Molecular Potentials forthe Prevision of Solvent Effects. Chem. Phys., 1981, 55 117.
54. Frisch M.J.; Trucks G.W.; Schlegel H.B.; Scuseria G.E.; Robb M.A.;Cheeseman J.R.; Montgomery Jr J.A.; 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.; KitaoO.; Nakai H.; Klene M.; Li X.; Knox J.E.; Hratchian H.P.; Cross J.B.;Bakken V.; Adamo C.; Jaramillo J.; Gomperts R.; Stratmann R.E.; YazyevO.; Austin A.J.; Cammi R.; Pomelli C.; Ochterski J.W.; Ayala P.Y.; MorokumaK.; Voth G.A.; Salvador P.; Dannenberg J.J.; Zakrzewski V.G.; DapprichS.; 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.; CliffordS.; Cioslowski J.; Stefanov B.B.; Liu G.; Liashenko A.; Piskorz P.; KomaromiI.; Martin R.L.; Fox D.J.; Keith T.; Al-Laham 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, GaussianInc, Wallingford CT, 2004.
55. Katritzky, A.R.; Jug, K.; Oniciu, D.C. Quantitative Measures of Aromaticityfor Mono-, Bi-, and Tricyclic Penta-and Hexaatomic Heteroaromatic RingSystems and Their Interrelationships. Chem. Rev., 2001, 101, 1421.
56. Cook, M.J.; Katritzky, A.R.; Linda, P. Aromaticity of Heterocycles. Adv. Heterocycl. Chem., 1974, 17, 255.
57. Hiberty, P.C.; Shaik, S.S.; Lefour, J.M.; Ohanessian, G. When does electronicdelocalization become a driving force of chemical bonding? J. Phys. Chem., 1988, 92, 5086.
58. Jug, K.; Köster, A. M. Influence of sigma. and pi electrons on aromaticity. J. Am. Chem. Soc., 1990, 112, 6772.
59. Kovacevic, B.; Baric, D.; Maksic, Z.B.; Müller, T. The Origin of Aromaticity:Important Role of the Sigma Framework in Benzene. ChemPhysChem,2004, 5, 1352.
60. Julg, A. In: Bergman, E.D.; Pullman B., Eds. Aromaticity, Pseudoaromaticity, Anti-aromaticity, Proceedings of an International Symposium, Jerusalem, Israel, March 31-April 3,1970; Israel Academy of Science andHumanities: Jerusalem, Israel, 1971.
61. Schleyer, P.V.R.; Freeman, P.K.; Jiao, H.; Goldfuss, B. The Cope RearrangementTransition Structure Is Not Diradicaloid, but Is It Aromatic?Angew. Chem. Int. Ed., 1995, 34, 337.
62. Krygowski, T.M.; Cyrański M. Separation of the Energetic and GeometricContributions to the Aromaticity. Part IV. A General Model for the x-Electron Systems. Tetrahedron, 1996, 30, 10255.
63. Pauling, L.J. Atomic Radii and Interatomic Distances in Metals. Am. Chem. Soc., 1947, 69, 542.
64. Bird, C.W. Heteroaromaticity. 8. the influence of N-oxide formation onheterocyclic aromaticity. Tetrahedron, 1993, 49, 8441.
65. Pozharski, A.F. Heteroaromaticity. Chem. Heterocycl. Comp., 1985, 21, 717.
66. Kotelevskii, S.I.; Prezhdo, O.V. Aromaticity indices revisited: refinementand application to certain five-membered ring heterocycles. Tetrahedron,2001, 57, 5715.
67. Jug, K. Bond Order Approach to Ring Current and Aromaticity. J. Org. Chem., 1983, 48, 1344.
68. Krygowski, T.M.; Ciesielski, A.; Bird, C.W.; Kotschy, A. Aromatic Characterof the Benzene Ring Present in Various Topological Environments inBenzenoid Hydrocarbons. Nonequivalence of Indices of Aromaticity. J. Chem. Inf. Comput. Sci., 1995, 35, 203.
69. Krygowski, T.M.; Anulewicz, R.; Kruszewski, J. Crystallographic studiesand physicochemical properties of p-electron compounds. III. Stabilizationenergy and the Kekulé structure contributions derived from experimentalbond lengths. Acta Crystallogr., 1983, B39, 732.
70. Ciesielski, A.; Krygowski, T.M.; Cyranski M.K.; Balaban, A. Defining rulesof aromaticity: a unified approach to the Hückel, Clar and Randić concepts. Phys. Chem., Chem. Phys., 2011, 13, 3737.
71. Proft de, F.; Geerlings, P. Conceptual and Computational DFT in the Studyof Aromaticity. Chem. Rev., 2001, 101, 1451.
72. Cyrański, M.K.; Schleyer, P.V.R.; Krygowski, T.M.; Jiao, H.; HohlneicherG. Facts and artifacts about aromatic stability estimation. Tetrahedron, 2003,59, 1657.
73. Wheeler, S.E.; Houk, K.N.; Schleyer, P.V.R.; Allen, W. D. A Hierarchy ofHomodesmotic Reactions for Thermochemistry. J. Am. Chem. Soc., 2009,131, 2547.
74. Dauben, H.J.; Wilson, J.D.; Laity, J.L. Diamagnetic Susceptibility Exaltationin Hydrocarbons. J. Am. Chem. Soc., 1969, 91, 1991.
75. Benson, R.C.; Flygare, W.H. Molecular Zeeman effect of cyclopentadieneand isoprene and comparison of the magnetic susceptibility anisotropies. J. Am. Chem. Soc., 1970, 92, 7523.
76. Gomes, J.A.N.F.; Mallion, R. B. Aromaticity and Ring Currents. Chem. Rev., 2001, 101, 1349.
77. Keith T.A.; Bader, R.F.W. Calculation of magnetic response properties usinga continuous set of gauge transformations. Chem. Phys. Lett., 1993, 210, 223.
78. Schleyer, P.V.R.; Jiao, H. What is aromaticity? Pure Appl. Chem., 1996, 68,209.
79. Stanger, A. Nucleus-Independent Chemical Shifts (NICS):-Distance Dependenceand Revised Criteria for Aromaticity and Antiaromaticity. J. Org. Chem., 2006, 71, 883.
80. Jiménez-Halla, J.O.C.; Matito, E.; Robles, J.; Solá, M. Nucleus-independentchemical shift (NICS) profiles in a series of monocyclic planar inorganiccompounds. J. Organomet. Chem., 2006, 691, 4359.
81. Foroutan-Nejad, C.; Shahbazian, S.; Rashidi-Ranjbar, P. The electron densityvs. NICS scan: a new approach to assess aromaticity in molecules with differentring sizes. Phys. Chem. Chem. Phys., 2010, 12, 12630.
82. zzScan: Measuring MagneticAromaticity among Molecules with Different Atom Types. J. Phys. Chem. A,2011, 115, 12708.
83. Ruud, K.; Helgaker, T.; Bak, K.L.; Jørgensen, P.; Jensen, H.J.A. Hartree-Fock Limit Magnetizabilities from London Orbitals. J. Chem. Phys., 1993,99, 3847.
84. Foroutan-Nejad, C.; Interatomic Magnetizability: A QTAIM-Based Approachtoward Deciphering Magnetic Aromaticity, J. Phys. Chem. A, 2011,115, 12555.
85. Poater, J.; Duran, M.; Solá, M.; Silvi, B. Theoretical Evaluation of ElectronDelocalization in Aromatic Molecules by Means of Atoms in Molecules(AIM) and Electron Localization Function (ELF) Topological Approaches. Chem. Rev., 2005, 105, 3911.
86. Fradera, X.; Austen, M.A.; Bader, R.F.W. The Lewis Model and Beyond. J. Phys. Chem. A, 1999, 103, 304.
87. Matta, C.F.; Hernandez-Trujillo, J. Application of the Quantum Theory ofAtoms in Molecules to Selected Physico-Chemical and Biophysical Problems:Focus on Correlation with Experiment. J. Phys. Chem. A, 2003, 107,7496.
88. Giambiagi, M.; de Giambiagi M. S.; dos Santos Silva, C. D.; Paiva de Figueiredo, A. Phys. Chem. Chem. Phys. 2000, 2, 3381.
89. Bultinck, P.; Ponec, R.; Van Damme, S. J. Phys. Org. Chem. 2005, 18, 706.
90. Bultinck, P.; Rafat, M.; Ponec, R.; van Gheluwe, B.; Carbo-Dorca, R.; Popelier, P. J. Phys. Chem. A 2006, 110, 7642;
91. Feixas, F.; Matito, E.; Sola, M.; Poate, J. J. Phys. Chem. A 2008, 112, 13231.
92. Merino, G.; Vela, A.; Heine, T. Description of Electron Delocalization viathe Analysis of Molecular Fields. Chem. Rev., 2005, 105, 3812.
93. Bader, R.F.W. Atoms in Molecules. A Quantum Theory, Clarendon Press:Oxford, 1994.
94. Bader, R. F. W. Density Functional Theory: A Source of Chemical Conceptsand a Cost-Effective Methodology for Their Calculation. Chem. Rev., 1991,91, 893.
95. Howard, S.T.; Krygowski, T.M. Benzenoid hydrocarbon aromaticity in termsof charge density descriptors. Can. J. Chem., 1997, 75, 1174.
96. Krygowski, T.M.; Ozimišski, W.P.; Ramsden, C.A. Sigma-and pi-electronstructure of aza-azoles. J. Mol. Model., 2010, 17, 1427.
97. Noorizadeh, S.; Shakerzadeh, E. Shannon entropy as a new measure ofaromaticity, Shannon aromaticity. Phys. Chem. Chem. Phys., 2010, 12, 4742.
98. Cyrašski, M.K.; Schleyer, P.V.R.; Krygowski, T.M.; Jiao, H.J.; Hohlneicher, G. Facts and artifacts about aromatic stability estimation. Tetrahedron, 2003,59, 1657.
99. Cysewski, P. Influence of thermal vibrations on aromaticity of benzene. Phys. Chem. Chem. Phys., 2011, 13, 12998.
100. Cysewski, P.; Jelišski, T. The ω-electron delocalization imposed by thermalvibrations of substituted benzene analogues in mediums of varying polarities. CMST, 2011, 17, 5.
101. Zalewski, R.I. in: Similarity Models in Organic Chemistry, Biochemistry andRelated Fields; Zalewski, R.I.; Krygowski, T.M.; Shorter J.; Elsevier:Amsterdam, 1991, 456.
102. STATISTICA (data analysis software system), version 9.0. www.statsoft.com
103. Alonso, M.; Miranda, C.; Martín, N.; Herradón, B. Chemical applications ofneural networks: aromaticity of pyrimidine derivatives. Phys. Chem. Chem. Phys., 2011, 13, 20564.
104. Fias, S.; van Damme, S.; Bultinck, P.J. Multidimensionality of delocalizationindices and nucleus independent chemical shifts in polycyclic aromatic hydrocarbons.J. Comput. Chem., 2008, 29, 358.