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]Ix11.7(H2O) (1), triclinic, P1, a = 10.2858(7) A, b = 11.3045(8) A, c = 20.808(1) A, alpha = 77.592(1) degrees, beta = 79.084(1) degrees, gamma = 77.684(1) degrees, Z = 2; [(Zr6BI12)]+[I(CH3OH)6]- (2), hexagonal, R3, a = 17.706(1) A, c = 13.910(1) A, Z = 3, [(Zr6CI12)(H2O)6]I(2).4(H2O) (3), triclinic, P1, a = 10.1566(5) A, b = 10.4513(5) A, c = 10.7549(6) A, alpha = 117.552(1) degrees, beta = 96.443(1) degrees, gamma = 96.617(1) degrees, Z = 1.