Peculiar antiaromatic inorganic molecules of tetrapnictogen in Na+Pn4- (Pn = P,As, Sb) and important consequences for hydrocarbons |
| |
Authors: | Kuznetsov Aleksey E Zhai Hua-Jin Wang Lai-Sheng Boldyrev Alexander I |
| |
Institution: | Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322, USA. |
| |
Abstract: | Although aromaticity has been observed in inorganic and all-metal species, the concept of antiaromaticity has not been extended beyond organic molecules. Here, we present theoretical and experimental evidence that the 6 -electron tetrapnictogen dianions in Na+Pn42- (Pn = P, As, Sb) undergo a transition from being aromatic to antiaromatic upon electron detachment, yielding the first inorganic antiaromatic Na+Pn4- molecules. Two types of antiaromatic structures were characterized, the conventional rectangular species and a new peculiar quasiplanar rhombus species. Aromaticity and antiaromaticity in the tetrapnictogen molecules were derived from molecular orbital analyses and verified by experimental photodetachment spectra of Na+Pn42-. On the basis of our findings for the tetrapnictogen clusters, we predicted computationally that the organic C4H4- anion also possesses two antiaromatic structures: rectangular and rhombus. Moreover, only the rhombus antiaromatic minimum was found for the radical NC3H4, thus extending the peculiar rhombus antiaromatic structure first uncovered in inorganic clusters into organic chemistry. |
| |
Keywords: | |
本文献已被 PubMed 等数据库收录! |
|