Open Access

Andreas John, Hans Bock

• Semiquinone radical anions are prototype compounds for contact ion pair formation with metal counter cations. In order to investigate the still open question whether bulky alkyl groups can sterically interfere, diphenoquinone derivatives O=C(RC=CH)2C=C(HC=CR)2C=O with R = C(CH3)3, CH(CH3)2 and CH3 have been selected and the following ESR/ENDOR results are obtained for the alkaline metal cations: The tetrakis(tert-butyl)-substituted radical anion only adds Li⊕ and Na⊕, while K⊕ forms no ion pair. The 3,3ʹ,5,5ʹ-tetra(isopropyl)diphenoquinone radical anion is accessible to all cations Me⊕, although Rb⊕ and Cs⊕ seem to be present solvent-separated in solution. The tetramethyl-substituted radical anion unfortunately polymerizes rapidly. Additional information concerns the ESR/ENDOR proof for ion triple radical cation formation [Li⊕ M•⊖Li⊕]•⊕, or the difference in the coupling constants upon Me⊕ docking at one δ⊖O=C group, suggesting that about 87% of the spin density is located in the cation-free molecular half of the diphenoquinone radical anion. Based on the wealth of ESR/ENDOR information, crystallization of the contact ion pairs and their structural characterization should be attempted.