Stabilization of Re37+/Re38+ Metalloclusters by Cyanide Ligands in New Trinuclear Rhenium Cluster Complexes [{Re3X3}(CN)9]4–/[{Re3X3}(CN)9]5– (X = Br or I)

Stabilization of Re37+/Re38+ Metalloclusters by Cyanide Ligands in New Trinuclear Rhenium Cluster Complexes [{Re3X3}(CN)9]4–/[{Re3X3}(CN)9]5– (X = Br or I) Full article

Journal

Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X

Output data

Year: 2021, Volume: 60, Number: 8, Pages: 5980-5987 Pages count : 8 DOI: 10.1021/acs.inorgchem.1c00399

Authors

Yarovoy Spartak S. ¹ , Gayfulin Yakov M. ¹ , Smolentsev Anton I. ¹ , Yanshole Vadim V. ² , Mironov Yuri V. ¹

Affiliations

1	Nikolaev Institute of Inorganic Chemistry SB RAS, 3, Acad. Lavrentiev Ave., Novosibirsk, 630090, Russia
2	International Tomography Center SB RAS, Institutskaya Str. 3A, Novosibirsk, 630090, Russia

The interaction of rhenium(III) halides Re3Br9 and Re3I9 with aqueous solution of sodium cyanide resulted in the formation of the first trinuclear halide–cyanide rhenium cluster complexes [{Re3X3}(CN)9]5–/[{Re3X3}(CN)9]4– (X = Br or I) crystallized as salts of the compositions Cs4Na[{Re3Br3}(CN)9]·5.25H2O (1), Cs4Na[{Re3I3}(CN)9]·6H2O (2), Cs4[{Re3Br3}(CN)9]·2H2O·0.5CsCl (3), and Cs4[{Re3I3}(CN)9]·(4). All of the compounds are stable in air in the solid state and in aqueous solution. The substitution of apical halide ligands in the parent compounds Re3X9 by cyanides led to reduction of the original metallocluster Re39+ (12 cluster valence electrons (CVEs)) to Re37+ (14 CVEs), forming the compounds 1 and 2. The apical CN– ligands affect the electronic structure of the Re3 metallocluster stabilizing reduced form. Complexes 1 and 2 represent the first examples of triangular rhenium clusters with the Re37+ metallocluster. The reaction of 1 and 2 with H2O2 resulted in formation of compounds 3 and 4 with the formal charge of the Re3 metallocluster equal to 8+, and no further oxidation to Re39+ occurred. The compounds were characterized by the X-ray diffraction analysis, NMR and UV–vis spectroscopies, mass spectrometry, cyclic voltammetry, and magnetic susceptibility measurements.

Yarovoy S.S. , Gayfulin Y.M. , Smolentsev A.I. , Yanshole V.V. , Mironov Y.V.
Stabilization of Re37+/Re38+ Metalloclusters by Cyanide Ligands in New Trinuclear Rhenium Cluster Complexes [{Re3X3}(CN)9]4–/[{Re3X3}(CN)9]5– (X = Br or I)
Inorganic Chemistry. 2021. V.60. N8. P.5980-5987. DOI: 10.1021/acs.inorgchem.1c00399 WOS Scopus РИНЦ OpenAlex

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