Coordination capacity of Keggin anions as polytopic ligands: case study of [VNb12O40]15− | Zendy

Anna A. Mukhacheva | Zendy; Victoria V. Volcheck | Zendy; Dmitriy G. Sheven | Zendy; Vadim V. Yanshole | Zendy; Nikolay B. Kompankov | Zendy; Mohamed Haouas | Zendy; Pavel A. Abramov⧫ | Zendy; Maxim N. Sokolov⧫ | Zendy

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Coordination capacity of Keggin anions as polytopic ligands: case study of [VNb₁₂O₄₀]¹⁵⁻

Author(s) -

Anna A. Mukhacheva,

Victoria V. Volcheck,

Dmitriy G. Sheven,

Vadim V. Yanshole,

Nikolay B. Kompankov,

Mohamed Haouas,

Pavel A. Abramov⧫,

Maxim N. Sokolov⧫

Publication year - 2021

Publication title -

dalton transactions

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.98

H-Index - 184

eISSN - 1477-9234

pISSN - 1477-9226

DOI - 10.1039/d1dt00765c

Subject(s) - ligand (biochemistry) , chemistry , crystallography , physics , stereochemistry , biochemistry , receptor

Reaction of Na9H4[VNb12O40{NbO(CO3)}2] with [(C6H6)RuCl2]2 (molar ratio {VNb12} : {(C6H6)Ru} = 1 : 4) in aqueous solution gives a mixture of [α-{(C6H6)Ru}4VNb12O40]7- and [α-{(C6H6)Ru}3VNb12O40]9-. Direct acetone diffusion into mother liquor leads to crystallization of Na6H[α-{(C6H6)Ru}4VNb12O40]·41.25H2O (1), characterized by single crystal X-ray diffraction (SCXRD). This anion has four organometallic fragments coordinated to the α-Keggin type [VNb12O40]15- backbone in different manner. Three {(C6H6)Ru}2+ groups cap triangular faces and one group a rectangular face of [VNb12O40]15-. Equilibrated mixture of [α-{(C6H6)Ru}4VNb12O40]7- and [α-{(C6H6)Ru}3VNb12O40]9- was studied by 1H DOSY NMR, HPLC-ICP-AES and HPLC-ESI-MS combined techniques. Direct chromatographic separation of these complexes results in unexpected transformation of both species into [α-{(C6H6)Ru}5VNb12O40]5-, isolated and characterized as Na5[α-{(C6H6)Ru}5VNb12O40]·16H2O (2). This anion contains five coordinated organometallic groups occupying both triangular and rectangular faces.

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