The first transition metal iodato peroxido complex: the synthesis, vibrational spectra and crystal structure from powder diffraction data of K3[V2O2(O2)4(IO3)]·H2O

Autor: Radovan Černý, Wouter van Beek, Ľubomír Smrčok, Peter Schwendt, Jana Chrappová, Mária Šimuneková
Rok vydání: 2013
Předmět:
Zdroj: Central European Journal of Chemistry, Vol. 11, No 8 (2013) pp. 1352-1359
Open Chemistry, Vol 11, Iss 8, Pp 1352-1359 (2013)
ISSN: 2391-5420
1895-1066
DOI: 10.2478/s11532-013-0266-8
Popis: The first transition metal iodato peroxido complex, K3[V2O2(O2)4(IO3)]·H2O (I), was prepared by crystallization from the KVO3 — KIO3 — H2O2 — H2O — ethanol (HNO3) solution. The dinuclear anion is immediately decomposed in aqueous solution; the 51V NMR spectrum exhibits signals corresponding to [VO(O2)2(H2O)]−, [V2O2(OH)(O2)4]3− and H2VO4− species only. The IR and Raman spectra contain all characteristic bands of the VO(O2)2 group and the coordinated IO3− ligand. Based on the positions of bands assigned to the vibrations of the VO(O2)2 groups a pentagonal pyramidal arrangement around the vanadium atoms can be supposed. The crystal structure was solved from X-ray synchrotron powder data by direct space method and refined by energy minimization in the solid state employing a hybrid PBE0 functional. This crystal and molecular structure, has confirmed the presence of hexacoordinated vanadium atoms and revealed asymmetric dinuclear structure of the [V2O2(O2)4(IO3)]3− ion. The coordination spheres of vanadium atoms are different — the IO3− anion is coordinated only to one vanadium center. A thermal analysis of the complex confirmed the presence of water molecules in the crystal structure and revealed a considerable stability of the dehydrated complex.
Databáze: OpenAIRE
Externí odkaz: