Coordination capacity of Keggin anions as polytopic ligands: Case study of [VNb12O40]15-

Anna A. Mukhacheva, Victoria V. Volcheck, Dmitry G. Sheven, Vadim V. Yanshole, Nikolay B. Kompankov, Mohamed Haouas, Pavel A. Abramov, Maxim N. Sokolov

Research output: Contribution to journalArticlepeer-review


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.

Original languageEnglish
Pages (from-to)7078-7084
Number of pages7
JournalDalton Transactions
Issue number20
Publication statusPublished - 25 May 2021




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