F. Diederich, P. J. Stang, R. R. Tykwinski 's acetylene chermistry PDF

By F. Diederich, P. J. Stang, R. R. Tykwinski

ISBN-10: 3527305181

ISBN-13: 9783527305186

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ISBN-13: 9783527306718

ISBN-10: 3527307133

ISBN-13: 9783527307135

ISBN-10: 3527307141

ISBN-13: 9783527307142

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TDDFT computations allow such a TICT to be inferred for the above N,N-dialkylaniline-substituted TEEs [204]. 22). Semiempirical PM3 calculations indicate that the planar all-s-trans conformation is not the most stable, and that slightly twisted s-cis and “U-shaped” geometries are preferred. This illustrates that effective p conjugation between adjacent CaC and CwC bonds does not require full planarity of the C4 fragment [207]. 22 (i Pr3 )Si n≤9 iso-PDA series Expanded dendralenes from reference [207].

7). The optimized geometry was recently reproduced at the B3LYP/6-31+G* level [121]: the ring strain was estimated to be quite weak (9 kcal mol–1) and the coordinating ability toward Li+ and Na+ was studied. 7, the angular strain is taken over by the sp carbon atoms and so might be further relieved by insertion of additional triple bonds. 10) was shown to experience reduced OITS and enhanced OITB, as simply predicted from the p donating properties and the Walsh orbitals of the cyclopropane rings [122].

The polyacetylenic character of C14, C18, and higher homologues was later confirmed at the RHF level of theory [187]. Finally, limited MCSCF or CCSD calculations from HF geometries, and quantum Monte Carlo calculations on C14 and C18, showed that electron correlation results in decreased bond length alternation but still favors polyacetylenic structures [188]. 14). x x For small C4n+2 molecules such as C6 (or C10), most calculation methods, including post-HF [188], indicate that they undergo bond angle alternation, but preserve bond length equalization.

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acetylene chermistry by F. Diederich, P. J. Stang, R. R. Tykwinski

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