Structure of the [Re12CS14(μ-SO2)(μ-O)2(CN)6]6– Cluster Anion

Abstract

A K[Ni(NH₃)₆]_2.5[Re₁₂CS₁₄(μ-O)₂(μ-SO₂)(CN)₆]·8H₂O compound (1) with a new [Re₁₂CS₁₄(μ-O)₂(μ-SO₂)(CN)₆]^6– cluster anion is prepared by the interaction of [Ni(NH₃)₆]_(aq)²⁺ with the products of incomplete substitution of μ-SO₂²⁻ ligands in the [Re₁₂CS₁₄(μ-SO₂)₃(CN)₆]^6– cluster anion and structurally characterized. New data on the effect of the ionic radius of the bridging μ-Q ligands on the geometric characteristics of the prismatic central {Re₃C(μ-Q)₃Re₃} unit of the bioctahedral cluster anions are obtained. The synthesis of compound 1 experimentally confirms the existence of stable intermediates in the μ-O^2– substitution reaction for the μ-SO₂²⁻ ligands of the [Re₁₂CS₁₄(μ-SO₂)₃(CN)₆]^6– anion and evidences that the reaction proceeds in steps.