Hexamethylphosphoric solvated electrons

High-energy irradiation of the lower alcohols gives solvated electrons, solvated protons and radicals [64]. Solvated electrons are also obtained by irradiation of the aprotic amide solvents [65] frequently used in organic electrochemistry and by the irradiation of hexamethylphosphoric triamide [66], N-Methylpyrrolidone which has properties similar to dimethylformaraide, is a useful solvent for the generation of solvated electrons because the reaction between electrons and protons is relatively slower than with dimethylformamide [67],... 

Hexamethylphosphor-triamide (HMPA) HMPA radical anion Solvated electron... 

While solvated electrons and their ion-pairs seem to be the most abundant species in liquid ammonia and hexamethylphosphoric-triamide, the negative alkali ions and their ion-pairs predominate in ethereal solvents. In fact, pulse radiolysis of tetrahydrofuran solutions of alkali tetraphenylborides revealed that the e, Met+ pairs, observed immediately after a pulse, rapidly decay, being converted into the corresponding Met" ions645. 

Phenyllithium is known to form, in equilibrium with the monomer, a dimer 25 (Scheme 1-21) held together by electron-deficient partial bonds. However, phenyllithium can also adopt the structure of a lithium lithiate ion pair 26 (Scheme 1-21). What makes the difference The solvent plays a capital role. As long as the solvation forces remain moderate as in diethyl ether, the doubly carbon-lithium-carbon bridged dimer 25 is energetically most favorable. In a 2 1 mixture of cylohexane and diethyl ether, phenyllithium even assembles a tetrameric cluster. " " in neat THF, the four-centered dimer 25 is found in equilibrium with the monomer. " However, in the presence of the powerful electron-donor hexamethylphosphoric triamide (HMPA), it is the ion pair 26 that coexists with the monomer. Analogous lithiate complexes have been identified with... 

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