ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Structures and Molecular Properties of Charge-Pertubed Molecules. 2, 3-Diphenylquinoxaline Radical Anions in Solution and in CrystalsThe Na⊕ and K⊕ radical-ion salts of 2, 3-diphenylquinoxaline seem to be (according to a structural database search) among the first ones of N-heterocyclic radical anions in crystals. The one-electron reduction in aprotic 1, 2-dimethoxyethan (DME) solution at metal mirrors and the crystallization under Ar have been preceded by cyclovoltammetric (CV) and ESR/ENDOR measurement. The first electron insertion at -1.63 V proves to be reversible, whereas the irreversible second step, which is accompanied by an overcrossing of the CV line, can be rationalized by an ‘ECE-DISP’ mechanism via a dianion redox disproportionation. The ENDOR spectrum resolves four 1H couplings and allows to simulate the ESR spectrum including the 14N hyperfine splittings. Both dark-blue single crystals of the radical ion salts \documentclass{article}\pagestyle{empty}\begin{document}$[2,3{\rm - diphenylquinoxaline}^{{.} \ominus} {\rm Met}^ \oplus ({\rm DME})]^.$\end{document} show unexpected similarities for Met⊕ = Na⊕, K⊕ despite the 36-pm difference in their ionic radii. The largest structural changes inflicted by the one-electron reduction of the N-heterocyclic molecule are observed in the vicinity of the N-centers bearing the highest effective nuclear charge. The DME-chelated metal cations coordinate at the N electron pairs and form Met⊕(DME)-bridged polymer chains of the radical anion, which are differently ondulated in the Na⊕ and K⊕ radical anion salts. The take-home lesson suggests that many more N-heterocyclic molecules might be analogously reduced under optimized conditions and isolated as single crystals.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19940770606
