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(NH<sub>3</sub>)<sub>6</sub>]<sub>2.5</sub>[Re<sub>12</sub>CS<sub>14</sub>(m-O)<sub>2</sub>(m-SO<sub>2</sub>)(CN)<sub>6</sub>]×8H<sub>2</sub>O compound (1) with a new [Re<sub>12</sub>CS<sub>14</sub>(m-O)<sub>2</sub>(m-SO<sub>2</sub>)(CN)<sub>6</sub>]<sup>6-</sup> cluster anion is prepared by the interaction of [Ni(NH<sub>3</sub>)<sub>6</sub>]<sub>(aq)</sub><sup>2+</sup> with the products of incomplete substitution of m-SO<sub>2</sub><sup>2-</sup> ligands in the [Re<sub>12</sub>CS<sub>14</sub>(m-SO<sub>2</sub>)<sub>3</sub>(CN)<sub>6</sub>]<sup>6-</sup> 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 {Re<sub>3</sub>C(m-Q)<sub>3</sub>Re<sub>3</sub>} unit of the bioctahedral cluster anions are obtained. The synthesis of compound 1 experimentally confirms the existence of stable intermediates in the m-O<sup>2-</sup> substitution reaction for the m-SO<sub>2</sub><sup>2-</sup> ligands of the [Re<sub>12</sub>CS<sub>14</sub>(m-SO<sub>2</sub>)<sub>3</sub>(CN)<sub>6</sub>]<sup>6-</sup> anion and evidences that the reaction proceeds in steps.