Destabilization of Conjugated Systems of α-Dicarbonyls and of Cyanogen

Andreas A. Zavitsas; Donald W. Rogers; Nikita Matsunaga

doi:10.1071/CH10394

RESEARCH ARTICLE

Previous Next Contents Vol 64(4)

Destabilization of Conjugated Systems of α-Dicarbonyls and of Cyanogen

Andreas A. Zavitsas ^A ^B , Donald W. Rogers ^A and Nikita Matsunaga ^A

+ Author Affiliations

- Author Affiliations

^A Department of Chemistry and Biochemistry, Long Island University, University Plaza, Brooklyn, NY 11201, USA.

^B Corresponding author. Email: zavitsas@liu.edu

Australian Journal of Chemistry 64(4) 390-393 https://doi.org/10.1071/CH10394
Submitted: 30 October 2010 Accepted: 22 November 2010 Published: 18 April 2011

Abstract

The formally conjugated system of α-carbonyls in 2,3-butanedione does not impart thermodynamic stabilization, but significant destabilization of 5.9 kcal mol^–1. The conjugated triple bonds of cyanogen cause a large thermodynamic destabilization of 11.4 kcal mol^–1, which is the difference in the enthalpies of hydrogenation of the first and second triple bonds. Experimental thermochemical and structural measurements and theoretical ab initio (G3) calculations support the destabilizations being reported. This work focuses only on the observable thermodynamic effects (enthalpies of hydrogenation), which are not necessarily related to the ability of conjugated groups to transmit electronic effects.

References

[1] H. Y. Afeefy, J. F. Liebman, S. E. Stein, Neutral Thermochemical Data, in NIST Chemistry Webbook, NIST Standard Reference Database No. 69 (Eds P. J. Linstrom, W. G. Mallard) (National Institute of Standards and Technology: Gaithersburg, MD 20899, USA) (http://webbbok.nist.gov).

[2] G. B. Kistiakowsky, J. R. Ruhoff, H. A. Smith, W. E. Vaughan, J. Am. Chem. Soc. 1936, 58, 146.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaA28Xht1Gksw%3D%3D&md5=d2fb3a46b8de8e6c4afb8c1eab7099faCAS |

[3] (a) L. Pauling, G. W. Wheland, J. Chem. Phys. 1933, 1, 362.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaA3sXktlaruw%3D%3D&md5=9b18fba9385cfa5723bf67a705f692c6CAS |
      (b) L. Pauling, J. Sherman, J. Chem. Phys. 1933, 1, 606.
      (c) L. Pauling, J. Sherman, J. Chem. Phys. 1933, 1, 679.
         | Crossref | GoogleScholarGoogle Scholar |

[4] W. Fang, D. W. Rogers, J. Org. Chem. 1992, 57, 2294.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK38Xhslegtr8%3D&md5=fa3153a856fb49c00afacc690767ea0eCAS |

[5] (a) D. W. Rogers, N. Matsunaga, A. A. Zavitsas, F. J. McLafferty, J.F. Liebman, Org. Lett. 2003, 5, 2373.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXksVylu7Y%3D&md5=d9ecc580fb7e3029eac9474e0fd48bf3CAS | 12841733PubMed |
      (b) D. W. Rogers, N. Matsunaga, F. J. McLafferty, A. A. Zavitsas, J. F. Liebman, J. Org. Chem. 2004, 69, 7143.
         | Crossref | GoogleScholarGoogle Scholar |

[7] M. D. Wodrich, C. Wannere, Y. Mo, P. D. Jarowski, K. N. Houk, P. von R. Schleyer, Chem. Eur. J. 2007, 13, 7731.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXhtFWktr3M&md5=059279ddedeb3d7d8b510e4cc834e62fCAS |

[8] D. Cappel, S. Tullmann, A. Krapp, G. Frenking, Angew. Chem. Int. Ed. 2005, 44, 3617.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXlsVyktLs%3D&md5=de2b4b0a345f97f748eec88ee75fa3a9CAS |

[10] K. Eriks, T. D. Hayden, S. H. Yang, I. Y. Chan, J. Am. Chem. Soc. 1983, 105, 3940.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL3sXktVGit7o%3D&md5=02729a5d4d72f352fc70a115591f9e76CAS |

[11] J. M. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr, T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian 03, revision B.04 2003 (Gaussian, Inc.: Pittsburgh, PA, USA).

[12] J. F. Liebman, Struct. Chem. 1992, 3, 449.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3sXlvFSnsQ%3D%3D&md5=4ec6632a9abf1a93f25301549c5471b4CAS |

[13] A. A. Zavitsas, J. Phys. Chem. A 2003, 107, 897.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXjsFKktQ%3D%3D&md5=8f065d155a8ce9d5544c659a590b1b12CAS |

[15] C. Hansch, A. Leo, R. W. Taft, Chem. Rev. 1991, 91, 165.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3MXhs1ehsLo%3D&md5=2001bcbad8b9872a190e08d2f4b11aa0CAS |

[17] D. D. Ebbing, S. D. Gammon, General Chemistry, 6th edn 1999 (Houghton Mifflin: Boston, MA, USA).

[18] C. E. Jakobsche, A. Choudhary, S. J. Miller, R. T. Raines, J. Am. Chem. Soc. 2010, 132, 6651.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXltFyrsbo%3D&md5=1cc247091951966cb6e798ef5f59732bCAS | 20420451PubMed |

[19] Experimental values cited in Computational Chemistry Comparison and Benchmark Database, release 15, 2010. NIST Standard Reference Database 101 (National Institute of Standards and Technology: Gaithersburg, MD 20899, USA) (http://cccbdb.nist.gov/).

[20] R. Notario, M. V. Roux, J. F. Liebman, Struct. Chem. 2010, 21, 481.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXls1CqtL0%3D&md5=e296b4db13e231a85d79fd8aff1c12f0CAS |

Destabilization of Conjugated Systems of α-Dicarbonyls and of Cyanogen

Abstract

References

Subscriber Login