Group 6 Oxyfluoro-Anion Salts of [XeF 5 ] + and [Xe 2 F 11 ] + : Syntheses and Structures of [XeF 5 ][M 2 O 2 F 9 ] (M=Mo, W), [Xe 2 F 11 ][M'OF 5 ] (M'=Cr, Mo, W), [XeF 5 ][HF 2 ]⋅CrOF 4 , and [XeF 5 ][WOF 5 ]⋅XeOF 4 .

Autor: Bortolus MR; Department of Chemistry, McMaster University, Hamilton, ON, L8S 4M1, Canada., Mercier HPA; Department of Chemistry, McMaster University, Hamilton, ON, L8S 4M1, Canada., Schrobilgen GJ; Department of Chemistry, McMaster University, Hamilton, ON, L8S 4M1, Canada.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2020 Jul 22; Vol. 26 (41), pp. 8935-8950. Date of Electronic Publication: 2020 Jul 01.
DOI: 10.1002/chem.202000826
Abstrakt: The reactions of the fluoride-ion donor, XeF 6 , with the fluoride-ion acceptors, M'OF 4 (M'=Cr, Mo, W), yield [XeF 5 ] + and [Xe 2 F 11 ] + salts of [M'OF 5 ] - and [M 2 O 2 F 9 ] - (M=Mo, W). Xenon hexafluoride and MOF 4 react in anhydrous hydrogen fluoride (aHF) to give equilibrium mixtures of [Xe 2 F 11 ] + , [XeF 5 ] + , [(HF) n F] - , [MOF 5 ] - , and [M 2 O 2 F 9 ] - from which the title salts were crystallized. The [XeF 5 ][CrOF 5 ] and [Xe 2 F 11 ][CrOF 5 ] salts could not be formed from mixtures of CrOF 4 and XeF 6 in aHF at low temperature (LT) owing to the low fluoride-ion affinity of CrOF 4 , but yielded [XeF 5 ][HF 2 ]⋅CrOF 4 instead. In contrast, MoOF 4 and WOF 4 are sufficiently Lewis acidic to abstract F - ion from [(HF) n F] - in aHF to give the [MOF 5 ] - and [M 2 O 2 F 9 ] - salts of [XeF 5 ] + and [Xe 2 F 11 ] + . To circumvent [(HF) n F] - formation, [Xe 2 F 11 ][CrOF 5 ] was synthesized at LT in CF 2 ClCF 2 Cl solvent. The salts were characterized by LT Raman spectroscopy and LT single-crystal X-ray diffraction, which provided the first X-ray crystal structure of the [CrOF 5 ] - anion and high-precision geometric parameters for [MOF 5 ] - and [M 2 O 2 F 9 ] - . Hydrolysis of [Xe 2 F 11 ][WOF 5 ] by water contaminant in HF solvent yielded [XeF 5 ][WOF 5 ]⋅XeOF 4 . Quantum-chemical calculations were carried out for M'OF 4 , [M'OF 5 ] - , [M' 2 O 2 F 9 ] - , {[Xe 2 F 11 ][CrOF 5 ]} 2 , [Xe 2 F 11 ][MOF 5 ], and {[XeF 5 ][M 2 O 2 F 9 ]} 2 to obtain their gas-phase geometries and vibrational frequencies to aid in their vibrational mode assignments and to assess chemical bonding.
(© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
Externí odkaz:
Nepřihlášeným uživatelům se plný text nezobrazuje