Skip to main content
SpringerLink
Log in

Quantum-chemical study of intramolecular electronic effects in phosphaalkenes

  • Published:
Theoretical and Experimental Chemistry Aims and scope

Abstract

The semiempirical CNDO/2 method has been used in a quantum-chemical study of the electronic and spatial structures of a series of phosphaalkenes as influenced by the nature of the substituents on the two-coordinated phosphorus atom and the carbon atom forming the P=C bond, as well as simple models for these. The data are compared with results from nonempirical calculations found in the literature for the latter. The authors discuss the effects of the substituents on the π-electron structures of the phosphaalkenes and the character of the outer orbitals. It is found that the d AO of phosphorus plays only a slight part in forming the bonds in these compounds. The electron-density distributions are close to those found for ethylene derivatives. The conclusions agree with spectral and structural studies on the phosphaalkenes.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

Literature cited

  1. E. Fluck, “Compounds of phosphorus with coordination number 2,” Topics Phosphor. Chem., 10, 193–284 (1980).

    Google Scholar 

  2. R. Appel, F. Knoll, and I. Ruppert, “Phospha-alkene und Phospha-alkine. Genese und Charakteristika ihrer (p-p)π-Mehrfachbindung,” Angew. Chem., 93, No. 9, 771–784 (1981).

    Google Scholar 

  3. T. A. van der Knaap, T. C. Klebach, F. Visser, et al., “Synthesis and structure of aryl-substituted phosphaalkenes”, Tetrahedron, 40, No. 4, 765–776 (1984).

    Google Scholar 

  4. M. J. Hopkinson, H. W. Kroto, J. F. Nixon, and N. P. C. Simmons, “The detection of unstable molecules by microwave spectroscopy: phosphaalkenes CF2=PH, CH2=PC1 and CH2=PH,” J. Chem. Soc. Chem. Communs., No. 13, 513–515 (1976).

    Google Scholar 

  5. R. Appel, F. Knoch, B. Laubach, and R. Sievers, “Niederkoordinierte P-Verbindungen 18,” Chem. Ber., 116. No. 5, 1873–1879 (1983).

    Google Scholar 

  6. A. N. Chernega, X-Ray Data on the Structures of Derivatives of Phosphorus with Coordination No. 2 and Reaction Products: PhD Thesis [in Russian], Moscow (1965).

  7. M. Yu. Antipin, Yu. T. Struchkov, et al., “The molecular structure of a new derivative of two-coordinated phosphorus: P-trimethyl-C-dimethylamino-C-diethylaminomethylene-phosphine,” Dokl. AN SSSR, 278, No. 5, 1146–1149 (1984).

    Google Scholar 

  8. Yu. T. Struchkov, A. N. Chernega, and M. Yu. Antipin, “Steric structures of two-coordinated phosphorus compounds,” Abstracts for the Eighth All-Union Conference on the Chemistry of Organophosphorus Compounds Dedicated to the Eightieth Anniversary of the Arbuzov Reaction, Kazan1, 13–16 May 1985 [in Russian], part 1, Kazan', p. 14.

  9. C. Thomson, “Electronic structure of phosphaalkenes,” J. Chem. Soc. Chem. Communs., No, 9, 522–523 (1977).

    Google Scholar 

  10. W. W. Schoeller and E. Niecke, “Frontier orbital crossing and ambident reactivity in P(III) systems with (p-p)π-bonds,” ibid., No. 11, 569–570 (1982).

    Google Scholar 

  11. D. Gonbeau, G. Pfister-Guillonzo, and J. Barrans, “Coordinence 2 du phosphore: etude quantochimique des systemes P=N et P=C,” Can. J. Chem., 61, No. 7, 1371–1378 (1983).

    Google Scholar 

  12. J. A. Pople and M. S. Gordon, “Molecular orbital theory of the electronic structure of organic compounds. 1. Substituent effects and dipole moments,” J. Am. Chem. Soc., 89, No. 17, 4253–4261 (1967).

    Google Scholar 

  13. A. S. Tarasevich, V. V. Pen'kovskii, and Yu. P. Egorov, “A CNDO/2 study of electronic structures in phosphazo compounds,” Teor. Eksp. Khim., 13, No. 5, 589–598 (1977).

    Google Scholar 

  14. V. G. Maslov, “A CNDO program for calculating molecular systems including up to 232 orbitals,” Zh. Strukt. Khim., 18, No. 2, 414–415 (1977).

    Google Scholar 

  15. M. W. Schmidt and M. S. Gordon, “Electronic structure of the phosphoryl and thiophosphoryl bonds,” J. Am. Chem. Soc., 107. No. 7, 1922–1930 (1985).

    Google Scholar 

  16. R. Appel, J. Peters, and A. Westerhaus, “Phosphaalkene durch termische, Basen- oder Metall-induzierte Eliminierung,” Tetrahedron Lett., 22, No. 49, 4957–4960 (1981).

    Google Scholar 

  17. V. D. Romanenko, T. V. Sarina, N. V. Kolotilo, and L. N. Markovskii, “C,C-bis(dialkyl-amino) methylenephosphones,” Zh. Obshch. Khim., 55, No. 5, 1188–1190 (1985).

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute of Organic Chemistry, Academy of Sciences of the Ukrainian SSR, Kiev

    V. V. Pen'kovskii & I. E. Boldeskul

Authors
  1. V. V. Pen'kovskii
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. I. E. Boldeskul
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 5, pp. 545–553, September–October 1986.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Pen'kovskii, V.V., Boldeskul, I.E. Quantum-chemical study of intramolecular electronic effects in phosphaalkenes. Theor Exp Chem 22, 520–526 (1987). https://doi.org/10.1007/BF00522536

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00522536

Keywords

Search

Navigation