What accounts for the remarkable difference between silabenzene and phosphabenzene in stability toward dimerization?

Organometallics

Volumn 19, Issue 11, 2000, Pages 2208-2214

  Brown, Eric C ^a   Borden, Weston Thatcher ^a  

^a UNIVERSITY OF WASHINGTON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001663736     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om0002172     Document Type: Article

References (51)

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26. See, inter alia: (a) Cherry, W.; Epiotis, N. D.; Borden, W. T. Acc. Chem. Res. 1977, 10, 167. (b) Feller, D.; Davidson, E. R.; Borden, W. T. J. Am. Chem. Soc. 1985, 107, 2596. (c) Coolidge, M. B.; Borden, W. T. J. Am. Chem. Soc. 1990, 112, 1704. (d) Coolidge, M. B.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1992, 114, 2354. (e) Johnson, W. T. G.; Borden, W. T. J. Am. Chem. Soc. 1997, 119, 5930. (f) Review: Borden, W. T. Chem. Commun. 1998, 1919.
27. See, inter alia: (a) Cherry, W.; Epiotis, N. D.; Borden, W. T. Acc. Chem. Res. 1977, 10, 167. (b) Feller, D.; Davidson, E. R.; Borden, W. T. J. Am. Chem. Soc. 1985, 107, 2596. (c) Coolidge, M. B.; Borden, W. T. J. Am. Chem. Soc. 1990, 112, 1704. (d) Coolidge, M. B.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1992, 114, 2354. (e) Johnson, W. T. G.; Borden, W. T. J. Am. Chem. Soc. 1997, 119, 5930. (f) Review: Borden, W. T. Chem. Commun. 1998, 1919.
28. See, inter alia: (a) Cherry, W.; Epiotis, N. D.; Borden, W. T. Acc. Chem. Res. 1977, 10, 167. (b) Feller, D.; Davidson, E. R.; Borden, W. T. J. Am. Chem. Soc. 1985, 107, 2596. (c) Coolidge, M. B.; Borden, W. T. J. Am. Chem. Soc. 1990, 112, 1704. (d) Coolidge, M. B.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1992, 114, 2354. (e) Johnson, W. T. G.; Borden, W. T. J. Am. Chem. Soc. 1997, 119, 5930. (f) Review: Borden, W. T. Chem. Commun. 1998, 1919.
29. See, inter alia: (a) Cherry, W.; Epiotis, N. D.; Borden, W. T. Acc. Chem. Res. 1977, 10, 167. (b) Feller, D.; Davidson, E. R.; Borden, W. T. J. Am. Chem. Soc. 1985, 107, 2596. (c) Coolidge, M. B.; Borden, W. T. J. Am. Chem. Soc. 1990, 112, 1704. (d) Coolidge, M. B.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1992, 114, 2354. (e) Johnson, W. T. G.; Borden, W. T. J. Am. Chem. Soc. 1997, 119, 5930. (f) Review: Borden, W. T. Chem. Commun. 1998, 1919.
30. See, inter alia: (a) Cherry, W.; Epiotis, N. D.; Borden, W. T. Acc. Chem. Res. 1977, 10, 167. (b) Feller, D.; Davidson, E. R.; Borden, W. T. J. Am. Chem. Soc. 1985, 107, 2596. (c) Coolidge, M. B.; Borden, W. T. J. Am. Chem. Soc. 1990, 112, 1704. (d) Coolidge, M. B.; Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1992, 114, 2354. (e) Johnson, W. T. G.; Borden, W. T. J. Am. Chem. Soc. 1997, 119, 5930. (f) Review: Borden, W. T. Chem. Commun. 1998, 1919.
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37. 298(PH3) = 5.5 kcal/mol, which is based on white phosphorus and was employed by Chase.
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39. (a) Coolidge, M. B.; Borden, W. T. J. Am. Chem. Soc. 1988, 110, 2298.
40. (b) A previous DFT study of the effect of substituents on Si-H BDEs has also been published: Wu, Y.-D.; Ling, C.-H. J. Org. Chem. 1995, 60, 821.
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47. This finding is not very surprising, since comparison of the angles between the P-H bond and the C-P-C plane in 1-phospha-2,4-cyclohexadiene (78.2°) and in phosphacyclohexane (77.9°) indicates that there is little conjugation between the lone pair of electrons on phosphorus and the double bonds in 1-phospha-2,4-cyclohexadiene. The P-C bond to the unsaturated carbon in 1-phospha-2,4-cyclohexadiene is 0.038 Å shorter than the P-C bond to the saturated carbon. However, most of this difference is almost certainly due to the difference in hybridization between these two carbons, rather than to P-C π bonding, since the two Si-C bond lengths o in 1-sila-2,4-cyclohexadiene actually differ by slightly more, 0.041 Å.
48. The 0.4 kcal/mol stabilizing interaction between the phosphorus lone pair and the adjacent double bond in 1-phospha-2,4-cyclohexadiene (eq 14) is, fortuitously, exactly canceled in eq 10 by the 0.4 kcal/mol greater delocalization energy of 1-phospha-2,4-cyclohexadienyl radical, relative to planar 1-sila-2,4-cyclohexadienyl radical (eq 15).
49. See, for example: (a) Nicolaides, A.; Borden, W. T. J. Am. Chem. Soc. 1991, 113, 6750. (b) Hrovat, D. A.; Duncan, J. A.; Borden, W. T. J. Am. Chem. Soc. 1999, 121, 169. (c) Reference 15e.
50. See, for example: (a) Nicolaides, A.; Borden, W. T. J. Am. Chem. Soc. 1991, 113, 6750. (b) Hrovat, D. A.; Duncan, J. A.; Borden, W. T. J. Am. Chem. Soc. 1999, 121, 169. (c) Reference 15e.
51. See, for example: (a) Nicolaides, A.; Borden, W. T. J. Am. Chem. Soc. 1991, 113, 6750. (b) Hrovat, D. A.; Duncan, J. A.; Borden, W. T. J. Am. Chem. Soc. 1999, 121, 169. (c) Reference 15e.