Bond-alternated and bond-equalized hexazine derivatives.

Planar cyclic conjugated molecules satisfying the Hückel rule are generally classified as aromatics and π delocalization is the key feature of aromatic compounds. It was shown that the π system of benzene prefers bond-alternation and that the delocalization observed is a consequence of bond-equalization, which is a σ effect. For systems wherein the π bonds are strong, such as those between N atoms, the π-distortivity may outweigh the σ preference for bond-equalization. Thus, one anticipates a bond-alternated structure for N6; however, neither the bond-equalized structure (D6h) nor the bond-alternated one (D3h) is a minimum as evident from the previous literature; calculations have shown that cyclic N6 is non-planar. Herein we show that a Lewis acid coordination strategy can be employed to stabilize the planar structure of N6. We show that the structure can be bond-alternated or bond-equalized depending on the strength of the Lewis acid. Kinetic stability with respect to concerted decomposition to three N-N triple bonded systems was assessed, and a few bond-equalized N6 systems were found to be potential candidates for synthesis.

Lewis Acidity Trend of Boron and Aluminium Trihalides: If Not π Back-Bonding, What Else?

Lewis acidity trend of boron trihalides is a subject that has received a variety of explanations, and still, the simple π back-bonding based one is believed by most, perhaps because of its simplicity, irrespective of opposing findings. Herein we try to give an alternative explanation based on qualitative Molecular Orbital (MO) theory and support that quantitatively by Generalized Kohn-Sham Energy Decomposition Analysis. While the role of orbital overlap on the orbital interaction energy is widely known, the role of electronegativity of the atoms involved is often overlooked. Here we find that the Lewis acidity trend of boron and aluminium halides can be explained by the Wolfsberg-Helmholz (W-H) formula for resonance integral. The MO theory-based predictions are valid only when the orbital interactions are strong enough. In weakly interacting systems, the effect of orbital interactions can be overshadowed by other effects such as Pauli repulsion, dispersion, etc. Thus the Lewis acidity trend of boron and aluminium halides can vary depending on the strength of the interacting Lewis base. We believe that this work would enable one to gain a better understanding not only on the Lewis acidity of boron trihalides and its heavy analogs but also on a variety of related problems such as the stronger π acidity of CS compared to CO and weaker π bonding between heavy atoms.

On the instability of iodides of heavy main group atoms in their higher oxidation state.

The inert pair effect-the tendency of the s orbital of heavy atoms to stay unreactive, is a consequence of the relativistic contraction of the s orbitals. While the manifestations of this on the reactivity depend on the nature of the substituents, this aspect is often overlooked. Divalent Pb prefers inorganic substituents, whereas tetravalent Pb prefers organic substituents. Among the inorganic substituents, again there are specific preferences-tetravalent Pb prefers F and Cl more than Br and I. It is as though the relativistic contraction of the s orbital of Pb is more significant with Br and I substituents than with Cl, F, and alkyl substituents. Herein, we address this problem using the molecular orbital approach and support it with quasi-relativistic density functional computations. We explain why typical hypervalent systems, like 12-X-6, and 10-X-5 (X is a heavy atom, the number preceding X is the number of valence electrons surrounding X, and the number after X is the coordination number) with less electronegative substituents carrying a lone pair (such as iodine), and Lewis octet molecules like PbI4 are unstable, but their dianions (14-X-6, 12-X-5, PbI42-) are not. For heavy atoms, the relativistic contraction of the s orbital renders the antibonding combination of s with ligand orbitals (σ1*) very low-lying, making it a good acceptor of electrons. Thus, compounds where σ1* is empty are kinetically unstable when an electron donor with appropriate energy (such as the lone pair on iodine or bromine) is present in the vicinity. Donor-acceptor interaction between σ1* and the lone pair on I or Br (F and Cl lone pairs are energetically far away from σ1*) is responsible for the instability of such compounds. The kinetic stability of tetraalkyl lead compounds is due to the absence of lone pairs on the alkyl substituents. This work illustrates the key factor responsible for the instability of heavy element iodides by taking into consideration the covalent nature of the bonds, while the existing explanations assume a purely ionic bonding, which is an oversimplification.

Alkyl Isosteres.

By substituting an ER3- unit (E = Group 13 element) or E'R3+ (E' = Group 15 element) for CR3 one gets to methyl isosteres, compounds analogous to alkyls and isoelectronic or iso-valence-electronic to them. The substituent charge can be used to stabilize countercharged aromatic systems; some compounds of this type are known. Nature makes available all kinds of escape routes to such formally zwitterionic species. Strategies for impeding the often facile reaction channels that open up can be designed. We construct what we believe are viable further examples of zwitterionic methyl isosteres based on 3-, 5-, 7-, and 8-membered rings. A similar strategy is laid out for dicationic and dianionic xylene isosteres.