Chalcogen versus dative bonding in [SF3] + Lewis acid−base adducts: [SF3(NCCH3)2] +, [SF3(NC5H5)2] +, and [SF3(phen)]+ (phen = 1,10-phenanthroline)

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dc.contributor.authorTurnbull, Douglas
dc.contributor.authorChaudhary, Praveen
dc.contributor.authorHazendonk, Paul
dc.contributor.authorWetmore, Stacey D.
dc.contributor.authorGerken, Michael
dc.date.accessioned2021-07-13T19:33:10Z
dc.date.available2021-07-13T19:33:10Z
dc.date.issued2021
dc.descriptionAccepted author manuscript.en_US
dc.description.abstractThe Lewis-acid behavior of [SF3][MF6] (M = Sb, As) salts toward mono- and bidentate nitrogen bases was explored. Reactions of [SF3][MF6] with excesses of CH3CN and C5H5N yielded [SF3(L)2]+ (L = CH3CN, C5H5N) salts, whereas the reaction of [SF3][SbF6] with equimolar 1,10-phenanthroline (phen) in CH3CN afforded [SF3(phen)][SbF6]·2CH3CN. Salts of these cations were characterized by low-temperature X-ray crystallography and Raman spectroscopy in the solid state as well as by 19F NMR spectroscopy in solution. In the solid state, the geometries of [SF3(NC5H5)2]+ and [SF3(phen)]+ are square pyramids with negligible cation–anion contacts, whereas the coordination of CH3CN and [SbF6]− to [SF3]+ in [SF3(NCCH3)2][SbF6] results in a distorted octahedral coordination sphere with a minimal perturbation of the trigonal-pyramidal SF3 moiety. 19F NMR spectroscopy revealed that [SF3(L)2]+ is fluxional in excess L at −30 °C, whereas [SF3(phen)]+ is rigid in CH2Cl2 at −40 °C. Density functional theory (DFT-B3LYP) calculations suggest that the S–N bonds in [SF3(NC5H5)2]+ and [SF3(phen)]+ possess substantial covalent character and result in a regular AX5E VSEPR geometry, whereas those in [SF3(NCCH3)2]+ are best described as S···N chalcogen-bonding interactions via σ-holes on [SF3]+, which is consistent with the crystallographic data.en_US
dc.description.peer-reviewYesen_US
dc.identifier.citationTurnbull, D., Chaudhary, P., Hazendonk, P., Wetmore, S. D., & Gerken, M. (2021). Chalcogen versus dative bonding in [SF3] + Lewis acid−base adducts: [SF3(NCCH3)2] +, [SF3(NC5H5)2] +, and [SF3(phen)]+ (phen = 1,10-phenanthroline). Inorganic Chemistry, 60, 3893-3901. https://dx.doi.org/10.1021/acs.inorgchem.0c03679?ref=pdfen_US
dc.identifier.urihttps://hdl.handle.net/10133/5955
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.urlhttps://dx.doi.org/10.1021/acs.inorgchem.0c03679?ref=pdfen_US
dc.subjectAdductsen_US
dc.subjectCrystal structureen_US
dc.subjectMathematical methodsen_US
dc.subject.lcshSulfur
dc.subject.lcshChalcogens
dc.subject.lcshLewis acids
dc.titleChalcogen versus dative bonding in [SF3] + Lewis acid−base adducts: [SF3(NCCH3)2] +, [SF3(NC5H5)2] +, and [SF3(phen)]+ (phen = 1,10-phenanthroline)en_US
dc.typeArticleen_US
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Hazendonk, Paul
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Wetmore, Stacey