Catalytic activation of C-H bonds in aromatic hydrocarbons, ethene, and methane by the naphthalene/sodium system in tetrahydrofuran

Angewandte Chemie (International Edition in English)

Volumn 35, Issue 21, 1996, Pages 2489-2491

  Rummel, Siegbert ^a   Ilatovskaya, Margarita A ^b   Mysov, Evgeny I ^b   Lenenko, Vladimir S ^b   Langguth, Helmuth ^a   Shur, Vladimir B ^b  

^a LEIBNIZ INSTITUTE OF SURFACE ENGINEERING IOM   (Germany)

^b A N NESMEYANOV INSTITUTE OF ORGANOELEMENT COMPOUNDS   (Russian Federation)

Author keywords

C H activation; H D exchange; Naphthalene sodium

Indexed keywords

EID: 0030477270     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199624891     Document Type: Article

References (15)

1. See, for example, M. Szwarc, Curbanions, Living Polymers and Electron Transfer Processes, Wiley-Interscience, New York, 1968.
2. With sodium/naphthalene ratios 1:1 and 2:1 naphthalene is formed as a result of a partial decomposition of naphthalene-sodium during the removal of THF.
3. The mass spectroscopic investigations were carried out on VG 7070 E and Trio 1000 (Fison) equipment. Ionization energies: 17.5eV for naphthalene, benzene, methane, and ethene, 8 eV for toluene.
4. S. M. Yunusow, M. A. Ilatovskaya, S. Rummel, M. Herrmann, E. I. Mysov, M. Wahren, V. B. Shur, M. E. Vol'pin, Izv. Akad. Nauk SSSR Ser. Khim. 1989, 1214.
5. M. A. Ilatovskaya, S. Rummel, Yu. V. Isaev, S. M. Yunusov, N. D. Lenenko, M. Herrmann, M. Wahren, Yu. N. Novikov, V. B. Shur, Izv. Akad. Nauk SSSR Ser. Khim. 1991, 1935.
6. Under these conditions cyclohexane is not involved in the H/D exchange.
7. D. C. Nonhebel, J. C. Walton, Free-Radical Chemistry. Structure and Mechanism, University Press, Cambridge, 1974.
8. It is improbable that the naphthalene dianion could play the part of the active species in the H/D exchange, because the dianion is not formed in the naphthalene/sodium system in THF, even in the presence of excess sodium [12].
9. For reports on the experimental detection of alkali metal clusters in the gas phase and in solid, inert gas matrices, and for quantum-chemical calculations of such cluster, see, for example. Metal Clusters (Ed.: M. Moskovitz), Wiley-Interscience, New York, 1986; B. Mile, P. D. Sillman, A. R. Yacob, J. A. Howard, J. Chem. Soc. Dalton Trans. 1996, 653-665; P. Fantucci, P. Balzarini, J. Mol. Catal. 1978, 4, 337-348; J. Flad, H. Stoll, H. Preuss, J. Chem. Phys. 1979, 71, 3042-3052.
10. For reports on the experimental detection of alkali metal clusters in the gas phase and in solid, inert gas matrices, and for quantum-chemical calculations of such cluster, see, for example. Metal Clusters (Ed.: M. Moskovitz), Wiley-Interscience, New York, 1986; B. Mile, P. D. Sillman, A. R. Yacob, J. A. Howard, J. Chem. Soc. Dalton Trans. 1996, 653-665; P. Fantucci, P. Balzarini, J. Mol. Catal. 1978, 4, 337-348; J. Flad, H. Stoll, H. Preuss, J. Chem. Phys. 1979, 71, 3042-3052.
11. For reports on the experimental detection of alkali metal clusters in the gas phase and in solid, inert gas matrices, and for quantum-chemical calculations of such cluster, see, for example. Metal Clusters (Ed.: M. Moskovitz), Wiley-Interscience, New York, 1986; B. Mile, P. D. Sillman, A. R. Yacob, J. A. Howard, J. Chem. Soc. Dalton Trans. 1996, 653-665; P. Fantucci, P. Balzarini, J. Mol. Catal. 1978, 4, 337-348; J. Flad, H. Stoll, H. Preuss, J. Chem. Phys. 1979, 71, 3042-3052.
12. For reports on the experimental detection of alkali metal clusters in the gas phase and in solid, inert gas matrices, and for quantum-chemical calculations of such cluster, see, for example. Metal Clusters (Ed.: M. Moskovitz), Wiley-Interscience, New York, 1986; B. Mile, P. D. Sillman, A. R. Yacob, J. A. Howard, J. Chem. Soc. Dalton Trans. 1996, 653-665; P. Fantucci, P. Balzarini, J. Mol. Catal. 1978, 4, 337-348; J. Flad, H. Stoll, H. Preuss, J. Chem. Phys. 1979, 71, 3042-3052.
13. For the decomposition of naphthalene-sodium in ethers into naphthalene and metallic sodium on strong dilution with hydrocarbon solvents, see N. D. Scott, J. F. Walker, V. L. Hansley, J. Am. Chem. Soc. 1936, 58, 2442 and Ref.[1].
14. N. M. Atherton, S. I. Weissman, J. Am. Chem. Soc. 1961, 83, 1330.
15. J. Smid, J. Am. Chem. Soc. 1965, 87, 655.