Solvated electrons, es-, have been generated in hexamethylphosphoric triamide (HMPA) by chemical and electrochemical means. W h e n Na metal was used to release es-, two distinct bands, already reported in the literature, appeared in t h e absorption spectrum of t h e solution, which rapidly turned red-brown and decomposed according to irreproducible complex kinetics which could not be analysed. When Li was used instead of sodium, a single broad band extending into t h e IR region developed and later decayed obeying consistently first-order kinetics in absorbance. Kinetic rate constants are reported and half-lives at ambient temperature were about 1 h duration. A systematic study of the disappearance of solvated electrons in HMPA was carried out at several temperatures (from 7 to 27°C) and an activation energy ( 8 H 9 kJ mol-') is estimated both in t h e absence and in the presence of lithium perchlorate. However, t h e overall reaction rate is markedly increased in the presence of Li' ; a mechanism is proposed to account for this lithium salt effect.
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