Non-isovalent Substitution in High-Valence Metal Cluster Complexes: Synthesis and Study of Re–W Heterometallic Clusters

Non-isovalent Substitution in High-Valence Metal Cluster Complexes: Synthesis and Study of Re–W Heterometallic Clusters Full article

Journal

Inorganic Chemistry
ISSN: 0020-1669

Output data

Year: 2026, Volume: 65, Number: 20, Pages: 11273–11284 Pages count : 12 DOI: 10.1021/acs.inorgchem.6c01067

Tags

Anions; Cluster chemistry; Metal clusters; Redox reactions; Tungsten

Authors

Gaifulina Viktoria K. ¹ , Sukhikh Taisiya S. ¹ , Ryzhikov Maxim R. ¹ , Gaifulin Yakov M. ¹ , Ulantikov Anton A. ¹ , Yanshole Vadim V. ² , Naumov Nikolay G. ¹

Affiliations

1	Nikolaev Institute of Inorganic Chemistry SB RAS, 3, Academician Lavrentiev Avenue, 630090 Novosibirsk, Russia
2	International Tomography Center SB RAS, 3A, Institutskaya Street, 630090 Novosibirsk, Russia

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.

Gaifulina V.K. , Sukhikh T.S. , Ryzhikov M.R. , Gaifulin Y.M. , Ulantikov A.A. , Yanshole V.V. , Naumov N.G.
Non-isovalent Substitution in High-Valence Metal Cluster Complexes: Synthesis and Study of Re–W Heterometallic Clusters
Inorganic Chemistry. 2026. V.65. N20. P.11273–11284. DOI: 10.1021/acs.inorgchem.6c01067 WOS Scopus OpenAlex

Submitted:	Feb 26, 2026
Accepted:	May 5, 2026
Published online:	May 14, 2026
Published print:	May 25, 2026

≡ Web of science:	WOS:001766930300001
≡ Scopus:	2-s2.0-105039983344
≡ OpenAlex:	W7161168212