Noble-Gas Difluoride Complexes of MOF 4 (M=Mo, W); Syntheses, Structures and Bonding of NgF 2  ⋅ MOF 4 and XeF 2  ⋅ 2MOF 4 (Ng=Kr, Xe).

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., Brock DS; 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] 2022 Mar 10; Vol. 28 (15), pp. e202103729. Date of Electronic Publication: 2022 Jan 14.
DOI: 10.1002/chem.202103729
Abstrakt: The NgF 2  ⋅ MOF 4 (Ng=Kr, Xe; M=Mo, W) and XeF 2  ⋅ 2MOF 4 complexes were synthesized in anhydrous HF (aHF) solvent and melts, respectively. Their single-crystal X-ray diffraction (SCXRD) structures show NgF 2  ⋅ MOF 4 and XeF 2  ⋅ 2MOF 4 have F t -Ng-F b - - -M arrangements, in which the NgF 2 ligands coordinate to MOF 4 through Ng-F b - - -M bridges. The XeF 2 ligands of XeF 2  ⋅ 2MOF 4 also coordinate to F 3 OM-F b '- - -M'OF 4 moieties through Xe-F b - - -M bridges to form F t -Xe-F b - - -M(OF 3 )-F b '- - -M'OF 4 , where XeF 2 coordinates trans to the M=O bond and F b ' coordinates trans to the M'=O bond. The Ng-F t , Ng-F b , and M- - -F b bond lengths of NgF 2  ⋅ nMOF 4 are consistent with MOF 4 and F 3 OM-F b '- - -M'OF 4 fluoride-ion affinity trends: CrOF 4 4 4 ≈F 3 OMo-F b '- - -Mo'OF 4 3 OW-F b '- - -W'OF 4 . The [- -(F 4 OMo)(μ 3 -F)H- - -(μ-F)H- -] ∞ solvate was also synthesized in aHF and characterized by SCXRD. Quantum-chemical calculations show the M- - -F b bonds of NgF 2  ⋅ MOF 4 and XeF 2  ⋅ 2MOF 4 are predominantly electrostatic, σ-hole type bonds.
(© 2021 Wiley-VCH GmbH.)
Databáze: MEDLINE
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