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HomeChemistryC2N2: a 10-electron four-atom molecule displaying each Hückel 4n+2 and Baird 4n...

C2N2: a 10-electron four-atom molecule displaying each Hückel 4n+2 and Baird 4n choice guidelines for ring aromaticity.

The earlier examples of 4 atom programs displaying two layers of aromaticity illustrated how 4 (B4), 8 (C4) and 12 (N4) valence electrons have been partitioned into 4n+2 manifolds (respectively 2+2, 6+2 and 6+6). The triplet state molecule B2C2 with 6 electrons partitioned into 2π and 4σ electrons, with the latter following Baird’s aromaticity rule.[1],[2]. Now for the ultimate lacking entry; as a triplet C2N2 has 10 electrons, which now partition into 4 + 6. However would that be 4π + 6σ or 4σ + 6π? Properly, in a method neither! Learn on.

The calculations (ωB97XD/Def2-TZVPP and CCSD(T)/Def2-TZVPP) are collected at FAIR DOI: 10.14469/hpc/10346. These present a partitioning into 5σ + 5π, a species that isn’t a minimal however undergoes a non-planar distortion.

Nevertheless, the primary excited state (the triplet) IS planar and is barely 12.5 kcal/mol above the planar 5+5 precursor. It’s now partitioned into 6σ and 4π, with the latter conforming to Baird’s rule for open shell triplets.[1],[2] So that is not like C2B2, which confirmed 2π + 4σ partitioning with the σ sequence following Baird’s rule. Now we’ve two examples through which one of many σ or the π-manifolds observe Baird’s rule and the opposite follows Hückel’s rule. The programs themselves are considerably contrived, however they present the easy enjoyable and video games that may be had with these aromaticity guidelines.

This publish has DOI: 10.14469/hpc/10350



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