Selective Oxidation of Inner Pnictogenide Ligands in Mixed-Ligand Rhenium Cubane-Type Cluster Complexes

Abstract

Reactivity of new tetrahedral rhenium cluster complexes with pnictogenide inner ligands μ₃-As^3-, μ₃-Sb^3-, and μ₃-Bi^3- has been investigated in reactions with aqueous H₂O₂. It has been found that the oxidation of clusters [{Re₄As₃Q}(CN)₁₂]^7- (Q = S or Se) led to the formation of stable clusters with μ₃-(AsO)^3- ligands. Under the same conditions, the oxidation of [{Re₄As₂S₂}(CN)₁₂]^6- cluster led to substitution of μ₃-As^3- ligands to μ₃-O^2-. The resulting cluster [{Re₄O₂S₂}(CN)₁₂]^4- easily undergoes further oxidation, and even at room temperature, a unique {Re₄} to {Re₃} rearrangement occurs with the formation of the new triangular cluster [{Re₃(μ₃-S)(μ-O)₂(μ-SO₂)}(CN)₉]^5-. Upon heating, this process proceeds faster and the triangular cluster can be isolated as individual compounds. Cluster anions [{Re₄SbSe₃}(CN)₁₂]^5- and [{Re₄BiS₃}(CN)₁₂]^5- reacted with H₂O₂, yielding clusters containing μ₃-O^2- ligands, namely, [{Re₄OSe₃}(CN)₁₂]^4- and [{Re₄OS₃}(CN)₁₂]^4-. This indicates that oxidized forms of μ₃-Sb^3- and μ₃-Bi^3- ligands can be easily substituted.