2019
DOI: 10.1002/ejic.201900595
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Lewis Acidic Behavior of MoOF4 towards the Alkali Metal Fluorides in Anhydrous Hydrogen Fluoride Solutions

Abstract: Previous studies performed on samples of MoOF4 dissolved in anhydrous hydrogen fluoride (aHF) solutions have indicated the presence of the [Mo2O2F9]– anion. Building upon this earlier work, MoOF4, and MF (M = Li–Cs) were dissolved in aHF solutions to produce M[Mo2O2F9] (M = Li–Cs) salts. Structural analysis of the obtained compounds was performed using single‐crystal X‐ray diffraction. This study provides the first single crystal structures for the [MoVI2O2F9]– anion. Additionally, IR and Raman spectroscopy we… Show more

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Cited by 25 publications
(39 citation statements)
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“…This becomes evident, as the Mo(3)−F(9) bond of 2.3161(13) Å is significantly longer than the Mo(1)−F(5) and Mo(2)−F(5) bonds of 2.1112(13) and 2.1071(13) Å, respectively. The latter nicely agree with the Mo−μ−F bond lengths in the alkali metal salts A [Mo 2 O 2 F 9 ] ( A =Li−Cs) [110] …”
Section: Resultssupporting
confidence: 73%
See 1 more Smart Citation
“…This becomes evident, as the Mo(3)−F(9) bond of 2.3161(13) Å is significantly longer than the Mo(1)−F(5) and Mo(2)−F(5) bonds of 2.1112(13) and 2.1071(13) Å, respectively. The latter nicely agree with the Mo−μ−F bond lengths in the alkali metal salts A [Mo 2 O 2 F 9 ] ( A =Li−Cs) [110] …”
Section: Resultssupporting
confidence: 73%
“…With a central cis ‐bridging [MoOF 5 ] polyhedron, two of the F atoms, F(5) and F(9), are μ‐bridging between the other two Mo atoms, resulting in the [Mo 3 O 3 F 13 ] − anion that can be described with the Niggli formula0[]MonormalF12normalF41normalO112MoF22F31O11- (Figure 13). Molybdenum oxide tetrafluoride, MoOF 4 , can also form other anions of different nuclearity with fluoride ion donors, such as the mononuclear [MoOF 5 ] − and the dinuclear [Mo 2 O 2 F 9 ] − anion [109,110] …”
Section: Resultsmentioning
confidence: 99%
“…They attributed these bands to hydrolysis species and suspected the bands occurring between 1000 and 1050 cm –1 to arise from the presence of the [Mo 2 O 2 F 9 ] – anion. We have recently reported a series of A [Mo 2 O 2 F 9 ] ( A = Li – Cs) salts having similar Mo–O stretching bands, however, we have not assigned the bands arising between 1000 and 1053 cm –1 to any particular anion. It is clear from the presence of these bands, however, that some hydrolysis has occurred.…”
Section: Resultsmentioning
confidence: 75%
“…A triple‐zeta‐valence + polarization (TZVP) level basis set was applied for F and Cl and split‐valence + polarization (SVP) level basis sets were applied for K, Rb and Cs. The basis sets were derived from the Karlsruhe def2 basis sets and taken from previous studies (F, Cl, K, Cs) or listed in the Supporting Information (Rb) . All calculations were carried out with the CRYSTAL17 program package .…”
Section: Methodsmentioning
confidence: 99%