ELECTRONIC STATES OF HOT IONS AND THE REACTIVITY OF [MOOCL3(DPPE)] TOWARDS SOLVATED ELECTRONS IN TRI-NORMAL-BUTYLPHOSPHATE

The reactivity of molybdenum(V) ions towards solvated electrons (e(s)-) was studied by spectroscopic analysis. The crystal-field parameters, Dq = 2470 cm-1, Ds = 6710 cm-1 and D-tau = 370 cm-1, for the complex [MoOCl3(dppe)] were determined and the energy terms were calculated. The mechanism of the reaction, involving the formation of the hot ion of [d(xy)]1[d(yz)]1 and [d(xy)]1[d(x)2-y2]1 configuration was suggested. The rate constant of the reaction of e(s)- with [MoOCl3(dppe)] [dppe = 1,2-bis-diphenyl-phosphineethane] was calculated as 4.5 x 10(10) dm3 mol-1 s-1. The higher reactivity of such a complex of cis-symmetry towards e(s)- was explained.