Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 25, Pages 13877-13881Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202103667
Keywords
2; 7-diazapyrene; antiaromaticity; electron-rich; reduction
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Funding
- MEXT, Japan [JP20H04668]
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The two-electron reduction of N,N'-dimethyl-2,7-diazapyrenium dications led to the formation of MDAP(0) with highly electron-rich 16 pi antiaromatic system. Experimental and theoretical results confirmed the antiaromatic character of MDAP(0) derived from its peripheral 16 pi-electron conjugation.
We describe the two-electron reduction of N,N '-dimethyl-2,7-diazapyrenium dications (MDAP(2+)), which afforded the corresponding reduced form (MDAP(0)) as a highly electron-rich 16 pi antiaromatic system. A single-crystal X-ray diffraction analysis of MDAP(0) revealed a distorted quinoidal structure with high bond-length alternation. The H-1 NMR spectrum of MDAP(0) exhibited a diagnostic proton signal (4.6 ppm) that is distinctly upfield shifted compared to that of aromatic diazapyrene (8.3 ppm). Theoretical calculations supported the existence of a paratropic ring current. These results indicate that MDAP(0) exhibits antiaromatic character derived from its peripheral 16 pi-electron conjugation.
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