Isolation of an Antiaromatic Singlet Cyclopentadienyl Zwitterion.

The reaction of triplet tetrachlorocyclopentadienylidene with BF in rare gas matrices yields a zwitterion consisting of a cyclopentadienyl cation bearing a positive charge and a negatively charged BF unit. IR and UV-vis spectra as well as the absence of EPR signals demonstrate a singlet ground state of the zwitterion, and its calculated geometry and magnetic properties clearly reveal a strong antiaromatic character. The zwitterion is highly labile and by visible or IR irradiation rearranges via a 1,2-fluorine migration from boron to carbon. Interaction with a second molecule of BF stabilizes the zwitterion and suppresses the fluorine migration, thus providing a convenient and efficient synthesis of an antiaromatic molecule under very mild conditions.