ic0488637_si_006.cif (27.08 kB)
Cluster Oxalate Complexes [M3(μ3-Q)(μ2-Q2)3(C2O4)3]2- and [Mo3(μ3-Q)(μ2-Q)3(C2O4)3(H2O)3]2- (M = Mo, W; Q = S, Se): Mechanochemical Synthesis and Crystal Structure
dataset
posted on 2005-04-04, 00:00 authored by Maxim N. Sokolov, Artyom L. Gushchin, Dmitrii Yu. Naumov, Olga A. Gerasko, Vladimir P. FedinMechanochemical reaction of cluster coordination polymers 1∞[M3Q7Br4] (M = Mo, W; Q = S, Se) with solid
K2C2O4 leads to cluster core excision with the formation of anionic complexes [M3Q7(C2O4)3]2-. Extraction of the
reaction mixture with water followed by crystallization gives crystalline K2[M3Q7(C2O4)3]·0.5KBr·nH2O (M = Mo,
Q = S, n = 3 (1); M = Mo, Q = Se, n = 4 (2); M = W, Q = S, n = 5 (3)). Cs2[Mo3S7(C2O4)3]·0.5CsCl·3.5H2O
(4) and (Et4N)1.5H0.5K{[Mo3S7(C2O4)3]Br}·2H2O (5) were also prepared. Close Q···Br contacts result in the formation
of ionic triples {[M3Q7(C2O4)3]2Br}5- in 1−4 and the 1:1 adduct {[Mo3S7(C2O4)3]Br}3- in 5. Treatment of 1 or 2 with
PPh3 leads to chalcogen abstraction with the formation of [Mo3(μ3-Q)(μ2-Q)3(C2O4)3(H2O)3]2-, isolated as (Ph4P)2[Mo3(μ3-S)(μ2-S)3(C2O4)3(H2O)3]·11H2O (6) and (Ph4P)2[Mo3(μ3-Se)(μ2-Se)3(C2O4)3(H2O)3]·8.5H2O·0.5C2H5OH (7).
All compounds were characterized by X-ray structure analysis. IR, Raman, electronic, and 77Se NMR spectra are
also reported. Thermal decomposition of 1−3 was studied by thermogravimetry.
