Two synthetic routes to bifunctional P(V)/P(V) compounds of the type EPR(2)NP(I)R(2) have been developed. The reaction of Li[EP(i)Pr(2)NP(i)Pr(2)] with one molar equivalent of I(2) produces EP(i)Pr(2)NP(I)(i)Pr(2) (3a-I, E = Se; 3b-I, E = Te). Alternatively, the oxidation of Na[N(P(t)Bu(2))(2)] with I(2) in tetrahydrofuran (THF) generates the P(III)/P(V) compound (t)Bu(2)PNP(I)(t)Bu(2) (6'-I) which, on treatment with elemental selenium or tellurium in THF, yields EP(t)Bu(2)NP(I)(t)Bu(2) (3a'-I, E = Se; 3b'-I, E = Te). The acyclic compounds 3a-I, 3a'-I, 3b-I, 3b'-I, and 6'-I have been characterized in solution by multinuclear ((1)H, (31)P, (77)Se, and (125)Te) NMR spectroscopy and in the solid state by X-ray structural determinations.
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