Abstract
The effects of substituents on the stability of 4-substituted(X) cub-1-yl cations (2), as well as the benchmark 4-substituted(X) bicyclo[2.2.2]oct-1-yl cation systems (7), for a set of substituents (X = H, NO2, CN, NC, CF3, COOH, F, Cl, HO, NH2, CH3, SiH 3, Si(CH3)3, Li, O-, and NH 3+) covering a wide range of electronic substituent effects were calculated using the DFT theoretical model at the B3LYP/6-311 + G(2d,p) level of theory. Linear regression analysis was employed to explore the relationship between the calculated relative hydride affinities (ΔE, kcal/mol) of the appropriate isodesmic reactions for 2/7 and polar field/group electronegativity substituent constants (σF and σχ, respectively). The analysis reveals that the ΔE values of both systems are best described by a combination of both substituent constants. This highlights the distinction between through-space and through-bond electronic influences characterized by σF and σχ, respectively.
Original language | English |
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Pages (from-to) | 513-516 |
Number of pages | 4 |
Journal | Journal of Physical Organic Chemistry |
Volume | 24 |
Issue number | 6 |
DOIs | |
Publication status | Published - Jun 2011 |
Keywords
- B3LYP/6-311 + G(2d,p)
- bicycle[2.2.2]octane
- cubane
- DFT
- electronic effects
- regression analysis
- substituent effects