Structure of the [Re<sub>12</sub>CS<sub>14</sub>(µ-SO<sub>2</sub>)(µ-O)<sub>2</sub>(CN)<sub>6</sub>]<sup>6-</sup> cluster anion
A K[Ni(NH3)6]2.5[Re12CS14(m-O)2(m-SO2)(CN)6]×8H2O compound (1) with a new [Re12CS14(m-O)2(m-SO2)(CN)6]6- cluster anion is prepared by the interaction of [Ni(NH3)6](aq)2+ with the products of incomplete substitution of m-SO22- ligands in the [Re12CS14(m-SO2)3(CN)6]6- cluster anion and structurally characterized. New data on the effect of the ionic radius of the bridging m-Q ligands on the geometric characteristics of the prismatic central {Re3C(m-Q)3Re3} unit of the bioctahedral cluster anions are obtained. The synthesis of compound 1 experimentally confirms the existence of stable intermediates in the m-O2- substitution reaction for the m-SO22- ligands of the [Re12CS14(m-SO2)3(CN)6]6- anion and evidences that the reaction proceeds in steps.