Lewis acid behavior of MoF5 and MoOF4: syntheses and characterization of MoF5(NCCH3), MoF5(NC5H5)n, and MoOF4(NC5H5)n (n- 1, 2)

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dc.contributor.authorBykowski, Janelle
dc.contributor.authorTurnbull, Douglas
dc.contributor.authorHahn, Nolan R. J.
dc.contributor.authorBoeré, René T.
dc.contributor.authorWetmore, Stacey D.
dc.contributor.authorGerken, Michael
dc.date.accessioned2022-10-24T22:21:20Z
dc.date.available2022-10-24T22:21:20Z
dc.date.issued2021
dc.descriptionAccepted author manuscripten_US
dc.description.abstractThe Lewis acid–base adducts MoF5(NC5H5)n and MoOF4(NC5H5)n (n = 1, 2) were synthesized from the reactions of MoF5 and MoOF4 with C5H5N and structurally characterized by X-ray crystallography. Whereas the crystal structures of MoF5(NC5H5)2 and MoOF4(NC5H5)2 are isomorphous containing pentagonal-bipyramidal molecules, the fluorido-bridged, heptacoordinate [MoF5(NC5H5)]2 dimer differs starkly from monomeric, hexacoordinate MoOF4(NC5H5). For the weaker Lewis base CH3CN, only the 1:1 adduct, MoF5(NCCH3), could be isolated. All adducts were characterized by Raman spectroscopy in conjunction with vibrational frequency calculations. Multinuclear NMR spectroscopy revealed an unprecedented isomerism of MoOF4(NC5H5)2 in solution, with the pyridyl ligands occupying adjacent or nonadjacent positions in the equatorial plane of the pentagonal bipyramid. Paramagnetic MoF5(NC5H5)2 was characterized by electron paramagnetic resonance (EPR) spectroscopy as a dispersion in solid adamantane as well as in a diamagnetic host lattice of MoOF4(NC5H5)2; EPR parameters were computed using ZORA with the BPW91 functional using relativistic all-electron wave functions for Mo and simulated using EasySpin. Density functional theory calculations (B3LYP) and natural bond orbital analyses were conducted to elucidate the distinctive bonding and structural properties of all adducts reported herein and explore fundamental differences observed in the Lewis acid behavior of MoF5 and MoOF4.en_US
dc.description.peer-reviewYesen_US
dc.identifier.citationLewis acid behavior of MoF5 and MoOF4: syntheses and characterization of MoF5(NCCH3), MoF5(NC5H5)n, and MoOF4(NC5H5)n (n- 1, 2). Inorganic Chemistry 60(20), 15695-15711. https://doi.org/10.1021/acs.inorgchem.1c02380en_US
dc.identifier.urihttps://hdl.handle.net/10133/6358
dc.language.isoen_USen_US
dc.publisherACS Publicationsen_US
dc.publisher.departmentDepartment of Chemistry and Biochemistryen_US
dc.publisher.facultyArts and Scienceen_US
dc.publisher.institutionUniversity of Lethbridgeen_US
dc.publisher.urlhttps://doi.org/10.1021/acs.inorgchem.1c02380en_US
dc.subjectAdductsen_US
dc.subjectLewis acidsen_US
dc.subjectLigandsen_US
dc.subjectMaterialsen_US
dc.subjectMetal organic frameworksen_US
dc.titleLewis acid behavior of MoF5 and MoOF4: syntheses and characterization of MoF5(NCCH3), MoF5(NC5H5)n, and MoOF4(NC5H5)n (n- 1, 2)en_US
dc.typeArticleen_US
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Boere, Rene
Gerken, Michael
Wetmore, Stacey