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The compounds ;p-Me2P(X)-C6H4-P(X)Me2, X = O, S, Se, NPh undergo one-electron reduction at a mercury cathode or on reaction with solvated electrons in a K/18-crown-6/THF mixture. The radical anions formed are persistent and have been characterized by ESR. They may be described as complexes of the spin-bearing moiety p-Me2P-C6H4-PMe2 · with the coordinated groups X.
The alkyls MR3 (M = B, AI, Ga, In) react with pyrazine (Pz) and sodium in THF to yield persistent radical complexes Pz(MR2)2 · +MR4- (1). Use of TIR3 leads to rapid deposition of thallium metal. The formation of these ionic complexes 1 is the result of MR3 dissociation into +MR2 and -MR4 ions. All radicals have been identified and characterized by ESR; the data reveal the influence of back bonding in the boron derivative.
The diphenyls MPh2 (M = Be, Mg, Zn, Cd, Hg) have been reacted with pyrazine (Pz) in tetrahydrofuran. Only the magnesium derivative undergoes electron transfer to yield the 1:1 radical complex [Pz(MgPh)]·. However, in the presence of sodium or potassium persistent 1:2 complexes [Pz(MPh)2]+. are formed with M = Be, Mg, Zn. Use of the higher homologues CdPh2 and HgPh2 leads to reduction to the metals. The 1:2 complexes have been characterized by ESR spectroscopy; metal coupling constants of 9Be, 25Mg and 67Zn could be determined in natural isotopic abundance.