[Ru₃(CN)₃(CO)₉]³⁻:Building Block for Multimetallic Cages

Abstract

A cluster‐ligand is disclosed in the form of [Ru3(CN)3(CO)9]3‐ ([1]3‐). Produced by simple reaction of [Ru3(CO)12] with cyanide, [1]3‐ serves as a precursor to a series of µ‐CN cages. When treated with [Ru3(CO)12], it readily forms the prism [Ru6(µ‐CN)3(CO)18]3‐. With 1.5 equiv of [Cu(MeCN)4]+ [1]3‐ reacts to give the expanded prism {Cu3[Ru3(µ‐CN)3(CO)9]2}3‐, which features three two‐coordinate Cu(I) centers. Sources of Ni2+ and Fe2+ bind two equivalents of [1]3‐, giving the double cages {M[Ru3(µ‐CN)3(CO)9]2}4‐ (M = Ni, Fe) wherein the central metal is octahedral. The 1:1 reaction using [Fe(H2O)6]2+ gave the interpenetrated super‐tetrahedrane {Fe4(µ4‐O)[Ru3(µ‐CN)3(CO)9]4}4‐.