Ab initio calculations of the effects of geminal silyl substituents on the stereomutation of cyclopropane and on the singlet-triplet splitting in trimethylene

Journal of the American Chemical Society

Volumn 120, Issue 28, 1998, Pages 7079-7084

  Skancke, Anne ^a,b   Hrovat, David A ^a   Borden, Weston Thatcher ^a  

^a UNIVERSITY OF WASHINGTON   (United States)

^b UNIVERSITY OF TROMSØ   (Norway)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOPROPANE; CYCLOPROPANE DERIVATIVE;

ARTICLE; CALCULATION; ENERGY; STEREOCHEMISTRY;

EID: 0032558155     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja980720u     Document Type: Article

References (48)

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35. 11a,b
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38. 17,21 the reaction in this equation is calculated to be energetically more favorable by CASPT2N calculations than by the R(O)HF/(2/2)CASSCF calculations that were used in ref 11b.
39. The difference between the values of +10.1 and -0.7 kcal/mol for the hyperconjugative stabilization energies of, respectively, 2c and 2a from the reaction in eq 4 is equal to the value of 10.8 kcal/mol that is obtained from the reaction in eq 2 after correcting it for twice the difference between the C-H BDEs of propane and 2,2-disilylpropane from the reaction in eq 3.
40. 2 in Table 1.
41. 1 combination of C-Si bonds at C(2) being highly cooperative in 2c. (29) The ΔZPE corrections in Table 1 are based on RHF frequencies for 1c and (2/2)CASSCF frequencies for all the other stationary points.
42. Another possible reaction of 1c on pyrolysis, cleavage of a C-Si bond, is computed to be endothermic by 88.9 kcal/mol at the (10/10)-CASPT2N level, so this process should not compete with any of the reactions that involve breaking C-C bonds in the three-membered ring. Cleavage of a C-Si bond in intermediate 2c is also computed to be endothermic at the (10/10)CASPT2N level, in this case by 18.6 kcal/mol.
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45. (c) Coolidge, M. B.; Borden, W. T. J. Am. Chem. Soc. 1988, 110, 2298.
46. s geometry was found to have two imaginary frequencies and an energy that was only 0.1 kcal/mol higher than either transition state. However, upon inclusion of dynamic electron correlation at the (10/10)CASPT2N level, the energy of the (0,0) geometry was calculated to be 0.8 kcal/mol lower than that of the conrotatory transition state and 1.4 kcal/mol lower than that of the monorotatory transition state.
47. 7
48. 3 groups should be at least qualitatively similar, but steric interactions between bulky trimethylsilyl groups at C(1) and substituents at C(2) and C(3) could be significant and thus might have an effect on the ratio of coupled to single rotation of the latter two carbons.