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)

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dc.contributor.authorTurnbull, Douglas
dc.contributor.authorChaudhary, Praveen
dc.contributor.authorLeenstra, Dakota
dc.contributor.authorHazendonk, Paul
dc.contributor.authorWetmore, Stacey D.
dc.date.accessioned2021-07-22T18:55:58Z
dc.date.available2021-07-22T18:55:58Z
dc.date.issued2020
dc.descriptionAccepted author manuscript.en_US
dc.description.abstractThe 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.description.peer-reviewYesen_US
dc.identifier.citationTurnbull, 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=pdfen_US
dc.identifier.urihttps://hdl.handle.net/10133/5965
dc.language.isoen_USen_US
dc.publisherAmerican Chemical Societyen_US
dc.publisher.departmentDepartment of Chemistry and Biochemistryen_US
dc.publisher.facultyArts and Scienceen_US
dc.publisher.institutionUniversity of Lethbridgeen_US
dc.publisher.institutionCanadian Centre for Research in Advanced Fluorine Technologiesen_US
dc.publisher.urlhttps://dx.doi.org/10.1021/acs.inorgchem.0c02783?ref=pdfen_US
dc.subjectAdducts
dc.subjectMetal organic frameworks
dc.subjectMathematical methods
dc.subjectLigands
dc.subject.lcshSalts
dc.subject.lcshLigands (Biochemistry)
dc.subject.lcshMetal-organic frameworks
dc.titleReactions 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.typeArticleen_US
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Hazendonk, Paul
Gerken, Michael
Wetmore, Stacey