ic050962c_si_008.pdf (16.3 kB)
Synthesis and Reactivity of W3Te74+ Clusters and Chalcogen Exchange in the M3Q7 (M = Mo, W; Q = S, Se, Te) Cluster Family
journal contribution
posted on 2005-10-31, 00:00 authored by Maxim N. Sokolov, Pavel A. Abramov, Artem L. Gushchin, Irina V. Kalinina, Dmitry Y. Naumov, Alexander V. Virovets, Eugenia V. Peresypkina, Cristian Vicent, Rosa Llusar, Vladimir P. FedinHeating WTe2, Te, and Br2 at 390 °C followed by extraction with KCN gives [W3Te7(CN)6]2-. Crystal structures of
double salts Cs3.5K{[W3Te7(CN)6]Br}Br1.5·4.5H2O (1), Cs2K4{[W3Te7(CN)6]2Cl}Cl·5H2O (2), and (Ph4P)3{[W3Te7(CN)6]Br}·H2O (3) reveal short Te2···X (X = Cl, Br) contacts. Reaction of polymeric Mo3Se7Br4 with KNCSe melt
gives [Mo3Se7(CN)6]2-. Reactions of polymeric Mo3S7Br4 and Mo3Te7I4 with KNCSe melt (200−220 °C) all give as
final product [Mo3Se7(CN)6]2- via intermediate formation of [Mo3S4Se3(CN)6]2-/[Mo3SSe6(CN)6]2- and of
[Mo3Te4Se3(CN)6]2-, respectively, as was shown by ESI-MS. (NH4)1.5K3{[Mo3Se7(CN)6]I}I1.5·4.5H2O (4) was isolated
and structurally characterized. Reactions of W3Q7Br4 (Q = S, Se) with KNCSe lead to [W3Q4(CN)9]5-. Heating
W3Te7Br4 in KCNSe melt gives a complicated mixture of W3Q7 and W3Q4 derivatives, as was shown by ESI-MS,
from which Ê3[W3(μ3-Te)(μ-TeSe)3(CN)6]Br·6H2O (5) and K5[W3(μ3-Te)(μ-Se)3(CN)9] (6) were isolated. X-ray analysis
of 5 reveals the presence of a new TeSe2- ligand. The complexes were characterized by IR, Raman, electronic,
and 77Se and 125Te NMR spectra and by ESI mass spectrometry.