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Original Articles

Principles of Phosphorus Chemistry: Molecular States of Phosphorus Compounds - A Report on Gasphase Investigations 1-3

Pages 3-53 | Published online: 04 Oct 2006

References

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  • Bock , H. , Solouki , B. and Binnewies , M. unpublished results.
  • Cf. e.g. “Gmelin Handbuch der Anorganischen Chemie: Phosphorus”, Vol. B-8, Verlag Chemie, Weinheim, 1964. For P = 0.19 and T = 1370 K the values α = 0.41 and In Kp/4 = −0.81 are reported.
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  • Hopkinson , M. J. , Kroto , H. W. , Nixon , J. F. and Simmons , N. P. 1976 . J. Chem. Soc. Chem. Commun. , : 513 Gasphase structure: B. Bak, N.S. Kristiansen and H. Svanholt, Acta Chem. Scand. Ser. A36, 1 (1982). In the mean-time, the synthesis has also been achieved by reaction of gaseous H3CPl2 with solid KOR, and the isolated compound could be characterized by NMR spectroscopy at 260 K: R. Carrie and J.-M. Denis (University Rennes), Abstr. CNRS Colloquium la Tour de Carol, May 1985.
  • Bock , H. and Ramsey , B. G. 1973 . PE Spectra of Main Group Element Compounds . Angew. Chem. , 85 : 773 Cf. the review by, Angew. Chem. Int. Ed. Engl. 12, 734 (1973).
  • Aue , D. H. , Webb , H. M. , Davidson , W. R. , Vidal , M. , Bowers , M. T. , Goldwhite , H. , Vertal , L. E. , Douglas , J. E. , Kollmann , P. A. and Kenyon , G. L. 1980 . J. Am. Chem. Soc. , 102 : 5151
  • Regitz , M. and Binger , P. 1988 . Angew. Chem. , 100 : 1541 Cf. also; Angew. Chem. Int. Ed. Engl. 27, 1484 (1988) or K. Karaghiosoff and A. Schmidtpeter, Phosphorus Sulfur, 36, 217 (1988).
  • Henderson , W. M. A. Jr. , Epstein , M. and Seichter , F. S. 1963 . J. Am. Chem. Soc. , 85 : 2462 A careful literature search revealed that cyclohexyl- and (3-pentyl)phosphane oxides upon heating at 60°C/1 torr, afford mixtures of products, from which tetraalkyltetraphosphetanes, (RP)4, can be isolated in small yields
  • 1989 . Scientific Symposium “125 Jahre Hoechst”, Festschrift Hoechst AG . : 72 Cf., e.g. the
  • Huheey , J. E. 1978 . “ Inorganic Chemistry: Principles of Structure and Reactivity ” . 839f New York : Harper and Row . Cf.
  • Gordon , M. S. , Boatz , J. A. and Schmidt , M. W. 1984 . J. Phys. Chem. , 88 : 2998 Calculations for substituted phosphane oxides XYHP=0 with X,Y = H, CH3, NH2, OR, F (ibid. 91, 1743 (1987)) suggest that the oxo forms are usually more stable than the hydroxy isomers XYP-OH and that the activation barrier for the isomerization H3P˭O →, H2POH should amount to approximately 300 kJ mol−1. Elimination of HX or XY has been proposed as a possible thermolysis pathway. Experimentally, the hydroxy form has been observed only for acceptor-substituted derivatives like (F3C2)P-OH (J.E. Griffith and A.B. Burg, J., Am. Chem. Soc., 84, 3442 (1962)) or on complex stabilization, e.g., in [(OC)4 HalMn←PR2OH] (E. Lindner and B. Schilling, Chem. Ber. 110, 3266 (1977)).
  • Vertical ionization energies of (CH3)2HP = O with assignment:22 10.32 eV (nO, πP˭O), 12.9 eV(σPC, σPH, σPO), and > 14.5 eV (σCH). For trans- 1,3-dimethyl-1,3-diphosphetane: m/z 120 (M⊕), 105 (M⊕-CH3), 92, 77, 75, 57, 45; IEV = 8.0 (4bg), 9.3 6ag), 11.3 (3bg, 3au, 5bu), 12.9 - 15.5 eV; ΔHf(MNDO) = −274.1 kJ mol−1
  • Bock , H. and Dammel , R. 1987 . Chem. Ber. , 120 : 1961 and literature quoted. For the preparatation of methane imines cf. J.C. Giullemin and J.- M. Denis, Angew. Chem., 94, 715 (1982); Angew. Chem. Int. Ed. Engl. 21, 690 (1982) and especially Angew. Chem. Suppl. 1982, 1515 as well as additional references given. For PE spectroscopic investigations see also J.B. Peel and G. Willet, J. Chem. Soc. Faraday Trans. 2, 71, 1799 (1975) or D.C. Frost, B. MacDonald, C.A. McDowell and N.P.C. Westwood, J. Electron Spectrosc. Relat. Phenom., 14, 379 (1978).
  • Dewar , M. J. S. , McKee , M. L. and Rzepa , H. S. 1978 . J. Am. Chem. Soc. , 100 : 3607 According to the literature, bond enthalpies of four-coordinate phosphorus(V) compounds obtained from MNDO calculations are usually too high, because d-polarization functions are not included in the MNDO parameter set (cf. On the other hand, ab initio studies,63 in agreement with the experimental data, indicate that nearly all derivatives HXYPO are 10 - 60 kJ mol−1 more stable than the corresponding tautomers XYPOH. According to the Hammond principle (J. Am, Chem. Soc. 77, 334 (1955)), the transition states of endothermic reactions should be product-like. Since these reactions are endothermic, therefore, the MNDO results of both the isomerization and the H2O elimination for the phosphorus(III) derivatives satisfactorily approximate this part of the energy hypersurface (Figure 19). For the phosphorus(V) compound (H3C)2HP˭O, the ab initio total energy63 has also been inserted (Figure: 19: O) to demonstrate that the potential well calculated by MNDO is too shallow.
  • Schmidt , M. W. , Yabushita , S. and Gordon , M. S. 1984 . J. Phys. Chem. , 88 : 32 Cf. e.g., as well as63 and C.J. Cramer, C.E. Dykstra and S.E. Denmark, Chem. Phys. Lett., 136, 17 (1987), who calculate isomerization barriers R2POH → R2HP = O of between 290 and 365 kJ mol−1
  • Bock , H. and Dammel , R. 1987 . Angew. Chem. , 90 : 518 For other examples of experimentally verified chemical activation, cf. Angew. Chem. Int. Ed. Engl. 26, 504 (1987) and references cited therein. The “chemically activated” H2C = NH, generated by methyl azide pyrolysis, eliminates H2 in the subsequent reaction channel and forms HCN at a temperature 500 K lower than after prior isolation in a 180 K cold trap.
  • Quadbeck-Seeger , H.-J. 1988 . Zwischen den Zeichen , Weinheim : VCH Verlagsges . Cf.

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