Excision of Zirconium Iodide Clusters from Highly Cross-Linked Solids

Highly cross-linked cluster precursors KZr6I14B, Zr6I12B, KZr6I14C, and Zr6I12C were successfully excised in
deoxygenated water, and the resulting red aqueous solutions of clusters exhibit better kinetic stability with respect
to decomposition than their chloride and bromide analogues. On traversing the Cl → I series, NMR measurements
show increasing deshielding of the interstitial atoms (Z = B, C) in Zr6ZX12 clusters and cyclic voltammetry
reveals increasingly positive reduction potentials for the [(Zr6BX12)(H2O)6]+ ions. Several new cluster complexes
have been crystallized from aqueous or methanolic solutions. Crystallographic data for these compounds are as
follows:  [(Zr6BI12)(H2O)6]I·11.7(H2O) (1), triclinic, P1̄, a = 10.2858(7) Å, b = 11.3045(8) Å, c = 20.808(1) Å,
α = 77.592(1)°, β = 79.084(1)°, γ = 77.684(1)°, Z = 2; [(Zr6BI12)]+[I(CH3OH)6]- (2), hexagonal, R3̄, a =
17.706(1) Å, c = 13.910(1) Å, Z = 3; [(Zr6CI12)(H2O)6]I2·4(H2O) (3), triclinic, P1̄, a = 10.1566(5) Å, b =
10.4513(5) Å, c = 10.7549(6) Å, α = 117.552(1)°, β = 96.443(1)°, γ = 96.617(1)°, Z = 1.