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dc.contributor.author Turnbull, Douglas
dc.contributor.author Chaudhary, Praveen
dc.contributor.author Leenstra, Dakota
dc.contributor.author Hazendonk, Paul
dc.contributor.author Wetmore, Stacey D.
dc.date.accessioned 2021-07-22T18:55:58Z
dc.date.available 2021-07-22T18:55:58Z
dc.date.issued 2020
dc.identifier.citation Turnbull, D., Chaudhary, P., Leenstra, D., Hazendonk, P., Wetmore, S. D., & Gerken, M. (2020). Reactions of molybdenum and tungsten oxide tetrafluoride with sulfur(IV) Lewis bases: structure and bonding in [WOF4]4, MOF4(OSO), and [SF3][M2O2F9] (M = Mo, W). Inorganic Chemistry, 59(23), 17544-17554.https://dx.doi.org/10.1021/acs.inorgchem.0c02783?ref=pdf en_US
dc.identifier.uri https://hdl.handle.net/10133/5965
dc.description Accepted author manuscript. Embargo in effect until Nov. 17, 2021 en_US
dc.description.abstract The structure of [WOF4]4 has been reinvestigated by low-temperature X-ray crystallography and DFT (MN15/def2- SVPD) studies. Whereas the W4F4 ring of the tetramer is planar and disordered in the solid state, the optimized gas-phase geometry prefers a disphenoidally puckered W4F4 ring and demonstrates asymmetric fluorine bridging. Dissolution of MOF4 (M = Mo, W) in SO2 and SF4 results in the formation of MOF4(OSO) and [SF3][M2O2F9], respectively. Both SO2 adducts and [SF3]- [Mo2O2F9] have been characterized by X-ray crystallography. The crystal structure of [SF3][Mo2O2F9] reveals dimerization of the ion pair that results in a rare heptacoordinate sulfur center. Optimization of the {[SF3][M2O2F9]}2 dimers in the gas phase, however, results in the elongation of one contact such that the sulfur centers are effectively hexacoordinate. Meanwhile, the crystal structure of [SF3][W2O2F9]·HF instead demonstrates hexacoordinate sulfur centers and a highly unusual coordination to [SF3]+ from [W2O2F9]−through an oxido ligand. While [SF3][W2O2F9] does not decompose at ambient temperature, MOF4(OSO) and [SF3][Mo2O2F9] are unstable toward evolution of SO2 or SF4. Computational studies reveal that the monomerization of [WOF4]4 in the gas phase at 25 °C is thermodynamically unfavorable using SO2, but favorable using SF4, consistent with the relative thermal stabilities of WOF4(OSO) and [SF3][W2O2F9].
dc.language.iso en_US en_US
dc.publisher American Chemical Society en_US
dc.subject Adducts
dc.subject Metal organic frameworks
dc.subject Mathematical methods
dc.subject Ligands
dc.subject.lcsh Salts
dc.subject.lcsh Ligands (Biochemistry)
dc.subject.lcsh Metal-organic frameworks
dc.title Reactions of molybdenum and tungsten oxide tetrafluoride with sulfur(IV) Lewis bases: structure and bonding in [WOF4]4, MOF4(OSO), and [SF3][M2O2F9] (M = Mo, W) en_US
dc.type Article en_US
dc.publisher.faculty Arts and Science en_US
dc.publisher.department Department of Chemistry and Biochemistry en_US
dc.description.peer-review Yes en_US
dc.publisher.institution University of Lethbridge en_US
dc.publisher.institution Canadian Centre for Research in Advanced Fluorine Technologies en_US
dc.publisher.url https://dx.doi.org/10.1021/acs.inorgchem.0c02783?ref=pdf en_US


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