Synthesis and Reactivity of W3Te74+ Clusters and Chalcogen Exchange in the M3Q7 (M = Mo, W; Q = S, Se, Te) Cluster Family
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- 作者：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 ; and Vladimir P. Fedin
- 刊名：Inorganic Chemistry
- 出版年：2005
- 出版时间：October 31, 2005
- 年：2005
- 卷：44
- 期：22
- 页码：8116 - 8124
- 全文大小：327K
- 年卷期：v.44,no.22(October 31, 2005)
- ISSN：1520-510X
文摘
Heating WTe2, Te, and Br2 at 390 
C followed by extraction with KCN gives [W3Te7(CN)6]2-. Crystal structures ofdouble 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 meltgives [Mo3Se7(CN)6]2-. Reactions of polymeric Mo3S7Br4 and Mo3Te7I4 with KNCSe melt (200-220 C) all give asfinal 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 isolatedand structurally characterized. Reactions of W3Q7Br4 (Q = S, Se) with KNCSe lead to [W3Q4(CN)9]5-. HeatingW3Te7Br4 in KCNSe melt gives a complicated mixture of W3Q7 and W3Q4 derivatives, as was shown by ESI-MS,from which Ê3[W3(
3-Te)(-TeSe)3(CN)6]Br·6H2O (5) and K5[W3(3-Te)(-Se)3(CN)9] (6) were isolated. X-ray analysisof 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.
C followed by extraction with KCN gives [W3Te7(CN)6]2-. Crystal structures ofdouble 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 meltgives [Mo3Se7(CN)6]2-. Reactions of polymeric Mo3S7Br4 and Mo3Te7I4 with KNCSe melt (200-220 C) all give asfinal 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 isolatedand structurally characterized. Reactions of W3Q7Br4 (Q = S, Se) with KNCSe lead to [W3Q4(CN)9]5-. HeatingW3Te7Br4 in KCNSe melt gives a complicated mixture of W3Q7 and W3Q4 derivatives, as was shown by ESI-MS,from which Ê3[W3(3-Te)(-TeSe)3(CN)6]Br·6H2O (5) and K5[W3(3-Te)(-Se)3(CN)9] (6) were isolated. X-ray analysisof 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.