Exceptionally Long Covalent CC Bonds—A Local Vibrational Mode Study

For decades one has strived to synthesize a compound with the longest covalent C−C bond applying predominantly steric hindrance and/or strain to achieve this goal. On the other hand electronic effects have been added to the repertoire, such as realized in the electron deficient ethane radical cation in its D3d form. Recently, negative hyperconjugation effects occurring in diamino-o-carborane analogs such as di-N,N-dimethylamino-o-carborane have been held responsible for their long C−C bonds. In this work we systematically analyzed CC bonding in a diverse set of 53 molecules including clamped bonds, highly sterically strained complexes such as diamondoid dimers, electron deficient species, and di-N,N-dimethylamino-o-carborane to cover the whole spectrum of possibilities for elongating a covalent C−C bond to the limit. As a quantitative intrinsic bond strength measure, we utilized local vibrational CC stretching force constants ka(CC) and related bond strength orders BSO n(CC), computed at the ωB97X-D/aug-cc-pVTZ level of theory. Our systematic study quantifies for the first time that whereas steric hindrance and/or strain definitely elongate a C−C bond, electronic effects can lead to even longer and weaker C−C bonds. Within our set of molecules the electron deficient ethane radical cation, in D3d symmetry, acquires the longest C−C bond with a length of 1.935 Å followed by di-N,N-dimethylamino-o-carborane with a bond length of 1.930 Å. However, the C−C bond in di-N,N-dimethylamino-o-carborane is the weakest with a BSO n value of 0.209 compared to 0.286 for the ethane radical cation; another example that the longer bond is not always the weaker bond. Based on our findings we provide new guidelines for the general characterization of CC bonds based on local vibrational CC stretching force constants and for future design of compounds with long C−C bonds.

A new strategy for hyperconjugative antiaromatic compounds utilizing negative charges: a dibenzo[b,f]silepinyl dianion

Herein we propose a new strategy for hyperconjugative antiaromatic compounds utilizing negative charges and have designed 5,5-diphenyldibenzo[b,f]silepinyl dianion (pseudo 16π-electron system), in which negative hyperconjugation occurs between the anionic π-cloud...

Impact of Electronic Effects on the Nucleofugality of Leaving Groups

A short review of the development of nucleofugality and electrofugality scales based on solvolysis rates of benzhydryl derivatives is presented. Accordingly, the rate of the heterolytic step in the SN1 displacement reaction and the leaving group ability (nucleofugality) in a given solvent are related with the special linear free-energy relationship (LFER) equation: log k = s f (N f + E f). The impact of electronic effects in the leaving group (nucleofuge) on the overall SN1 reactivity of the substrate is given. The importance of inductivity, resonance, polarity and field effects in the leaving group moiety in the transition state is analyzed. Also, the effect of the negative hyperconjugation and the influence of other electronic effects in the leaving group on the height of the reaction intrinsic barrier are considered.1 Introduction2 Development of the Nucleofugality Scale3 Inductive and Resonance Effects4 Negative Hyperconjugation5 Intrinsic Barrier6 Conclusions