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Impact of the Exchange of the Coordinating Solvent Shell in [Bi38O45(OMc)24(dmso)9] by Alcohols: Crystal Structure, Gas Phase Stability, and Thermoanalysis

ZAAC18

ZAAC18

M. Weber, G. Thiele, E. Dornsiepen, D. P. Weimann, C. A. Schalley, S. Dehnen, M. Mehring – 2018

Recrystallization of the bismuth oxido cluster [Bi38O45(OMc)24(dmso)9]·2dmso·7H2O (A) (OMc = O2C4H5) from alcohols such as EtOH and iPrOH gave single crystals of the bismuth oxido clusters [Bi38O45(OMc)24(ROH)x(H2O)y] [R = Et, x = 13, y = 0 (1); R = iPr, x = 10, y = 2 (2)]. Both compounds crystallize in the triclinic space group P1¯ and exhibit minor deviations in their cell parameters [1: a = 17.0156(5) Å, b = 19.0048(5) Å, c = 20.2100(5) Å, α = 111.182(2) °, β = 111.475(2) °, γ = 100.716(2) °, V = 5275.7(3) Å3; 2: a = 17.2512(7) Å, b = 19.3712(7) Å, c = 19.6248(8) Å, α = 112.803(3) °, β = 105.969(3) °, γ = 100.183(3) °, V = 5507.08(40) Å3]. ESI-MS studies show that the bismuth oxido clusters 1 and 2 are more easily desolvated as reported for the dmso adduct A. Collision-induced dissociation (CID) experiments on the solvent free cluster ions reveal a new fragmentation path for the methacrylate ligands. They split into C3H4 fragments as the leaving group and a formate remains bound at the cluster core. Bismuth particles are formed after annealing of 1 at 300 °C, whereas a composite consisting of Bi/β-Bi2O3/C was formed in the temperature range of 400 °C to 600 °C. Calcination of 1 at 300 °C and 400 °C provided the formation of an amorphous material containing bismuth and a composite composed of β-Bi2O3/Bi2O2CO3/ Bi/C, respectively. At higher calcination temperatures, α-Bi2O3 was obtained. The decomposition products do not show any sulfate incorporation as observed for A.

Title
Impact of the Exchange of the Coordinating Solvent Shell in [Bi38O45(OMc)24(dmso)9] by Alcohols: Crystal Structure, Gas Phase Stability, and Thermoanalysis
Author
M. Weber, G. Thiele, E. Dornsiepen, D. P. Weimann, C. A. Schalley, S. Dehnen, M. Mehring
Date
2018
Citation
Z. Anorg. Allg. Chem. 2018, 644, 1796.
Type
Text