화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.131, No.28, 9789-9799, 2009
Homoconjugation/Homoaromaticity in Main Group Inorganic Molecules
Quantum chemical computations show that three groups of inorganic ions and neutral molecules, whose structures have long been known and characterized, are aromatic due to through-space homoconjugation: (i) I-4(2+), S6N42+, and S2I42+ dications and the (O-2)(4) cluster with pericyclic transition-state-like (PTS-like) homoaromaticity; (ii) the bishomoaromatic Te-6(2+) and 1,5-diphosphadithiatetrazocines; and (iii) the spherically homoaromatic Te-6(4+). The S2I42+ dication has an unusually high S-S bond order (similar to 2.3) and dual PTS-like aromaticity arising from two separate sets of four-center, six-electron (4c-6e) in-plane through-space conjugation. The diamagnetic (O-2)(4) structural unit recently observed in epsilon-phase oxygen solid has quadruple PTS-like aromaticity, each arising from 4c-6e in-plane through-space conjugation within an O-2-O-2 plane. Finally, we note that the lighter S-6(4+) and Se-6(4+) homologues of Te-6(4+) also are spherically homoaromatic and might be observable in complexes.