Group The Alkali and Coinage Metals

Hydrocarbon Radical Anion and Dianion Alkali-Metal Compounds.— The orystal structure of (Ph—Ph), K+(tetraglyme)2 is essentially the same as that of the Rb analogue the cations are surrounded by ten oxygens of the two tetraglyme molecules. The effect of pressure on the ion-pair equilibria, solvent-separated ion-pair (s.s.i.p.)v contact ion-pair (c.i.p.), for Naph, Na+ in THF was studied as was the volume change for the conversion c.i.p. - s.s.i.p. Disproportionation equilibria [equation (1)] were variously studied, e.g. for ArH = perylene (Pe),  

Reactions of ArH % M+ with alkyl halides and proton sources have attracted further attention. The same isomeric mixture of RLi was produced from Naph %-Li+ in THF at room temperature and l-Br-cts,cis-2,3-Me2-cyclopropane (c,c-RX) or its transttrans-isomsr (r,r-RX). Hence trapping of RX , Li+ was not encountered because of its very rapid decomposition (to R ), or alternatively dissociative electron transfer takes place to give R directly. Furthermore, equilibration of the s-cyclopropyl radicals, R must occur at a faster rate than their reaction with Naph %Li+ to give the configurationally stable RLi. Complex separated ion-pairs, Anth, D, K+ e.g, D = dicyclohexano-18-crown-6) are protonated by EtOH in a pseudo first-order process, which is several orders of magnitude slower than the pseudo first-order protonation of the c.i.p. form. A claim by Stevenson et al. that reaction of Naph , Na+ and H2O provides Naph, OH , and H2 has been disputed the reaction followed by Stevenson was argued to have been that of Na rather than Naph-, Na+. 

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