Synthesis and crystal structures of (pyH)2[Mo2O4F6] and (pipH2)[Mo2O4F6]; vibrational band assignment for [Mo2O4F6]2− anion

• Published in: Journal of fluorine chemistry Vol. 156; pp. 240 - 245
• Main Authors: Veryasov, Gleb, Morozov, Dmitry, Goreshnik, Evgeny, Jesih, Adolf
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01-12-2013
• Subjects: Anions; Banded structure; Crystal structure; DFT calculations; Diffraction; Fluorinated ethylene propylenes; Mathematical analysis; Molybdenum coordination compounds; Oxyfluorides; Raman spectroscopy; Synthesis (chemistry); X-ray diffraction; X-rays; Molybdenum coordination compounds; X-ray diffraction; Oxyfluorides; Raman spectroscopy; DFT calculations
• ISSN: 0022-1139; 1873-3328
• DOI: 10.1016/j.jfluchem.2013.10.012

The compounds (pyH)2[Mo2O4F6] and (pipH2)[Mo2O4F6], (Py=pyridine, pip=piperazine), were synthesized by the reaction of MoBr3Py3 and [Mo(CO)5]pip with anhydrous HF in a FEP reaction vessel. The compounds were characterized by X-ray diffraction and Raman spectroscopy; band assignment for the anion [Mo2O4F6]2− was made basing on DFT/B3LYP/cc-PVDZ calculations.
•The synthesis of two novel MOF compounds – (pyH)2[Mo2O4F6] and (pipH2)[Mo2O4F6] was made.•Compounds were characterized by X-ray diffraction and Raman spectroscopy.•Detailed vibrational band assignment for [Mo2O4F6]2− anion was made based on computed spectrum.
The two closely related compounds (pyH)2[Mo2O4F6] and (pipH2)[Mo2O4F6], (Py=pyridine, pip=piperazine), were synthesized by the reaction of MoBr3Py3 and [Mo(CO)5]2pip with anhydrous HF in a FEP (fluorinated ethylene propylene) reaction vessel. The presence of traces of water resulted in the formation of oxyfluorides. (pyH)2[Mo2O4F6] and (pipH2)[Mo2O4F6] were characterized by X-ray diffraction and Raman spectroscopy. Geometry of the anion [Mo2O4F6]2− was optimized using DFT/B3LYP with cc-PVDZ basis set and the interpretation of the measured Raman spectra was offered based on normal modes of calculated spectrum.