Synthesis and structural characterization of [HxCp*TiMo5O18](3−x)− (x=0, 1, 2); new insights into protonation patterns in polyoxometalates

Autor: Atsushi Yagasaki, M. Hashimoto, Haruo Akashi, H. Hasegawa, T. Sakuraba, Jinzhu Chen, T. Hashimoto
Rok vydání: 2003
Předmět:
Zdroj: Polyhedron. 22:2847-2854
ISSN: 0277-5387
DOI: 10.1016/s0277-5387(03)00411-x
Popis: Reaction of [(n-C4H9)4N]2[Mo2O7], Cp*TiCl3, and [(n-C4H9)4N]OH in CH3CN yields [(n-C4H9)4N]3[Cp*TiMo5O18]·CH3CN [a=12.863(4) A, b=26.608(6) A, c=24.534(4) A, β=103.88(2)°, Z=4, space group P21/c (no. 14)]. Similar reaction without [(n-C4H9)4N]OH yields monoprotonated complex [(n-C4H9)4N]2[HCp*TiMo5O18], where, according to a single-crystal X-ray diffraction study [a=19.9550(4) A, b=25.5420(8) A, c=11.8820(3) A, β=100.31(2)°, Z=4, space group P21/n (no. 14)], the anion is protonated at one of OMo2 doubly-bridging oxygens. Reaction of [(n-C4H9)4N]2[HCp*TiMo5O18] with CCl3COOH in CHCl3 followed by crystallization from CH3CN/Et2O yields diprotonated [(n-C4H9)4N][H2Cp*TiMo5O18]·1/4(C2H5)2O, which, according to a single-crystal X-ray diffraction study [a=12.319(2) A, b=16.105(3) A, c=12.001(2) A, α=110.74(1)°, β=100.31(2)°, γ=82.777(5), Z=2, space group P 1 (no. 2)], contains hydrogen-bonded dimers of [H2Cp*TiMo5O18]− ions. The [Cp*TiMo5O18]3− is basic enough to form stable organometallic adducts like [(η-C8H12)Ir(Cp*TiMo5O18)]2− and [(η-C8H14)Rh(Cp*TiMo5O18)]2−.
Databáze: OpenAIRE
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