Barthelat, Trinquier, Bertrand
/ Some SlCiH4 Isomers
G. Davies and B. P. Roberts in "Free Radicals", Vol. I, J. K. Kochi, Ed., Wiley, New York, 1973,Chapter 10. (8)(a) K. U. Ingold. Chem. Comrnun., 91 l'(1969);(b) A. G. Davies, K. U. Ingold, B. P. Roberts, and R. Tudor, J. Chem. Soc. 6,698 (1971):(c) S.Korcek. G. B. Watts, and K. U. Ingold, J. Chem. Soc., Perkin Trans. 2, 242 (1972); (d) J. Grotewold, E. A. Lissi, and J. C. Scaiano, J. Chem. Soc. 6,475(1969): (e) A. G. Davies, D. Griller, and B. P. Roberts, ibid., 1823 (1971);(1) A. G. Davies, T. Maki, and B. P. Roberts, J. Chem. SOC., Perkin Trans. 2, 744 (1972):(9) A. G. Davies, D. Griller, B. P. Roberts, and R. Tudor, Chem. Commun., 640 (1970);(h) J. Grotewold, E. A. Lissi, and J. C. Scaiano, J. Chem. SOC.8, 1187 (1971);( i ) A. G. Davies and J. C. Scaiano, J. Chem. SOC.,Perkin Trans. 2, 2234 (1972). (9)P. J. Krusic and J. K. Kochi, J. Am. Chem. Soc.,91,3942(1969);J. K. Kochi and P. J. Krusic, "Essays on Free-Radical Chemistry", Chem. SOC.Spec. fubl. No. 24 (1970). (IO) H. C. Brown, "Hydroboration", W. A. Benjamin, New York, 1962;T. 8. Eames and B. M. Hoffman, J. Am. Chem. Soc., 93,3141(1971). (11) H. Paul, R. D. Small, Jr., and J. C. Scaiano, J. Am. Chem. Soc., 100,4520
(1978). (12)C. Walling and P. J. Wagner, J. Am. Chem. Soc., 85,2333 (1963);88,3368 (1964).
3785 (13)R. D. Small, Jr., and J. C. Scaiano, J. fhys. Chem., 81, 828, 2126 (1977). (14)T. Shida and W. H. Hamill, J. Chem. fhys., 44, 2369 (1966). (15)K. Adamic, D. F. Bowman, T. Gillan, and K. U. Ingoid, J. Am. Chem. SOC., 93,902 (1971). (16)The difficulty appears to arise in part from the low solubility of Ph3B in difert-butvl oeroxide.
(17)M. Venthi, A. Brescia, F. Busi, and Q. G. Mulazzani, Inf. J. Radiaf. Phys. Chem.. a. 673 (1976). (18)D. H. Ellison, G.'A. Salmon, and F. Wilkinson, Roc. R. SOC.London, Ser. A, 328, 23 (1972),and references cited therein. (19)A. G. Davies and J. C. Scaiano, J. Chem. SOC.,Perkin Trans. 2, 2234 (1972). (20)C. Walllng and M. S. Pearson, J. Am. Chem. Soc., 86,2262 (1964). (21)Recent results indicate that difference in the rates of @-scissionbetween PhP(0Et)zOBu-f and f-BuOP(OEt)3 may be small (see also ref 5). We are grateful to Dr. B. P. Roberts for the communication of unpublished work. (22)L. K. Patterson and J. Lilie, lnf. J. Radiat. fhys. Chem., 6 , 129 (1974);R. H. Schuler and G. K. Buzzard, ibid., 8,563 (1976). (23)G. Ferraudi, horg. Chem., 17, 1370 (1978).
Theoretical Investigations on Some C2SiH4 Isomers Jean-Claude BartheIat,*la Georges Trinquier,la and Guy BertrandIb Contributionfrom the Laboratoire de Physique Quantique and Laboratoire des Organom&alliques, Uniuersit6 Paul Sabatier, 31 077 Toulouse Cedex, France. Received December 4, 1978
Abstract: A p a r t o f the CZSiH4 potential energy surface has been explored using a nonempirical pseudopotential method. T h e silacyclopropene (3) and silacyclopropylidene computed relative stabilities of the five isomers, silylacetylene (0 kcal/mol) (2) (both I 7 kcal/mol) 2-silaallene (46 kcal/mol) < 2-silapropyne (61 kcal/mol), d i f f e r significantly f r o m those of the analogous carbon compounds: propyne allene < cyclopropene
