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The reaction of the K4[Re6Si8(OH)a6]·8H2O rhenium cluster salt with pyrazine (Pz) in aqueous solutions of alkaline or alkaline earth salts at 4 °C or at room temperature leads to apical ligand exchange and to the formation of five new compounds [trans-Re6Si8(Pz)a2(OH)a2(H2O)a2] (1), [cis-Re6Si8(Pz)a2(OH)a2(H2O)a2] (2), (NO3)[cis-Re6Si8(Pz)a2(OH)a(H2O)a3](Pz)·3H2O (3), [Mg(H2O)6]0.5[cis-Re6Si8(Pz)a2(OH)a3(H2O)a]·8.5H2O (4), and K[cis-Re6Si8(Pz)a2(OH)a3(H2O)a]·8H2O (5). Their crystal structures are built up from trans- or cis-[Re6Si8(Pz)a
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