Probing the influence of anomeric effects on the lithium ion affinity in 1,3-diaza systems: a computational study

Lithium ion affinities of methanediamine (MDA), N,N,N',N'-tetramethylmethanediamine (TMMDA), 1,3-diazacyclohexane (DAC), trans-3,5-diazabicyclo[4.4.0]decane (trans-3,5-DBD), trans-1,3-diazabicyclo[4.4.0]decane (trans-1,3-DBD), cis-1,3-diazabicyclo[4.4.0]decane (cis-1,3-DBD), 1,5-diazabicyclo[3.3.1]nonane (DBN), trans-decahydro-8a,9a-diazaanthracene (trans-DDA), cis-decahydro-8a,9a-diazaanthracene (cis-DDA), 1,3-diazetidine (DAT), 1,3-imidazolidine (IMD), and 1,3-diazepane (DAP) have been studied by using density functional theory (DFT) and correlated ab initio methods. Possible conformers of these compounds were optimized at the B3LYP/6-31+G* level, and relative energies were evaluated at the MP2/6-311+G**//B3LYP/6-31+G* level. The experimental lithium ion affinities for reference molecules (i.e., ammonia and trimethylamine) are well-reproduced at these levels of theory. NBO analysis shows the influence of anomeric effects (n(N) → σ*(C-N) hyperconjugative interactions) on the conformational stability of the title compounds; however, the electrostatic and steric contributions included in the NBO Lewis term also affect the stabilities in some cases. The influence of anomeric effect is apparent in cis-DDA, where the nitrogen involved in n(N) → σ*(C-N) hyperconjugative interaction (cis-DDA-Li2) has a lithium ion affinity 1.7 kcal/mol lower than the nitrogen not involved in n(N) → σ*(C-N) hyperconjugative interaction (cis-DDA-Li1). In general, the computed lithium ion affinities were found to be conformationally dependent. The NBO results showed that the lithium ion affinities are also governed by the interplay of n(N) → σ*(C-N) hyperconjugative interactions and the steric strain caused upon lithiation. Further, the ring size also influences the lithium ion affinities in the 1,3-diaza monocyclic systems. In some complexes multiple coordination of the lithium ion is possible by inversion of one of the nitrogen atoms.