Polynuclear bismuth-oxo clusters: insight into the formation process of a metal oxide

The reaction of the bismuth silanolates [Bi(OSiR2R')3] (R = R' = Me, Et, iPr; R = Me, R' = tBu) with water has been studied. Partial hydrolysis gave polynuclear bismuth-oxo clusters whereas amorphous bismuth-oxo(hydroxy) silanolates were obtained when an excess of water was used in the hydrolysis reaction. The metathesis reaction of BiCl3 with NaOSiMe3 provided mixtures of heterobimetallic silanolates. The molecular structures of [Bi18Na4O20(OSiMe3)18] (2), [Bi33NaO38(OSiMe3)24].3 C7H8 (3.3 C7H8), [Bi50Na2O64(OH)2(OSiMe3)22].2 C7H8.2H2O (4.2 C7H8.2 H2O), [Bi4O2(OSiEt3)8] (5), [Bi9O7(OSiMe3)13].0.5 C7H8 (6. 0.5C7H8), [Bi18O18(OSiMe3)18)].2C7H8 (7. 2C7H8) and [Bi20O18(OSiMe3)24].3C7H8 (8.3C7H8) are presented and compared with the solid-state structures of [Bi22O26(OSiMe2tBu)14] (9) and beta-Bi2O3. Compound 2 crystallises in the triclinic space group P1 with the lattice constants a = 17.0337(9), b = 19.5750(14), c = 26.6799(16) A, alpha = 72.691(4), beta = 73.113(4) and gamma = 70.985(4) degrees ; compound 3.3C7H8 crystallises in the monoclinic space group P2(1)/n with the lattice constants a = 20.488(4), b = 22.539(5), c = 26.154(5) A and beta = 100.79(3) degrees ; compound 4.2C7H82 H2O crystallises in the monoclinic space group P2(1)/n with the lattice constants a = 20.0518(12), b = 24.1010(15), c = 27.4976(14) A and beta = 103.973(3) degrees ; compound 5 crystallises in the monoclinic space group P2(1)/c with the lattice constants a = 25.256(5), b = 15.372(3), c = 21.306(4) A and beta = 113.96(3) degrees ; compound 6.0.5C7H8 crystallises in the triclinic space group P1 with the lattice constants a = 15.1916(9), b = 15.2439(13), c = 22.487(5) A, alpha = 79.686(3), beta = 74.540(5) and gamma = 66.020(4) degrees ; compound 7.2C7H8 crystallises in the triclinic space group P1 with the lattice constants a = 14.8295(12), b = 16.1523(13), c = 18.4166(17) A, alpha = 75.960(4), beta = 79.112(4) and gamma = 63.789(4) degrees ; and compound 8.3C7H8 crystallises in the triclinic space group P1 with the lattice constants a = 17.2915(14), b = 18.383(2), c = 18.4014(18) A, alpha = 95.120(5), beta = 115.995(5) and gamma = 106.813(5) degrees . The molecular structures of the bismuth-rich compounds are related to the CaF2-type structure. Formally, the hexanuclear [Bi6O8]2+ fragment might be described as the central building unit, which is composed of bismuth atoms placed at the vertices of an octahedron and oxygen atoms capping the trigonal faces. Depending on the reaction conditions and the identity of R, the thermal decomposition of the hydrolysis products [Bi(n)O(l)(OH)(m-)(OSiR3)(3n-(2l-m))] gives alpha-Bi2O3, beta-Bi2O3, Bi12SiO20 or Bi4Si3O12.