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![The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F54498.jpg&w=3840&q=50)
The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique
Published on: November 28, 2016
Non-isovalent Substitution in High-Valence Metal Cluster Complexes: Synthesis and Study of Re-W Heterometallic
Viktoria K Gaifulina1, Taisiya S Sukhikh1, Maxim R Ryzhikov1
1Nikolaev Institute of Inorganic Chemistry SB RAS, 3, Academician Lavrentiev Avenue, 630090 Novosibirsk, Russia.
None:
A previously unexplored reaction of ReSe2 and WSe2 in a KCN melt resulted in the formation of the heterometallic cluster products, namely, the salt K5[Re5WSe8(CN)6] and the chain polymer K6[Re3.6W2.4Se8(CN)4(CN)2/2]. Oxidative depolymerization and the differences in redox behavior of the complexes enabled the isolation of soluble salts of the cluster anions [Re5WSe8(CN)6]4-, [Re4W2Se8(CN)6]4-, and [Re3W3Se8(CN)6]4- with TBA+ cations as individual crystalline compounds. A comparative study of the complexes shows that sequential substitution of rhenium atoms in the cluster core with electron-deficient tungsten atoms leads to periodic variations in the physicochemical properties of the clusters. This is reflected, for instance, in a cathodic shift of the redox potentials and in the greater number of accessible charge states. At the same time, DFT calculations indicate that the octahedral cluster geometry for electron-precise complexes is almost insensitive to the number of tungsten atoms and undergoes local distortions upon variation of the cluster skeletal electron count.
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