Controlled hydrolysis of the hexafluorides of molybdenum, tungsten and rhenium: structure of oxonium (.mu.-fluoro)bis(tetrafluorooxotungstate(VI))

Abstract

T10TeF5(mes)2]2 and [Tl(mes)2+][B(OTeF5)4'] are in harmony with the molecular structures for these compounds. There are mutually exclusive IR and Raman v(TeO) bands for [TIO-TeF5(mes)2]2, consistent with the nearly centrosymmetric structure of this dimer. The average v(TeO) value of 823 cm'1 is between the low value for HOTeF5 (733 cm"1) and the high value for [N(«-Bu)4+][OTeF5'] (867 cm'1) and correlates well with the Te-0 distances and for this compound (Table VIII). The compound T10TeF5 also exhibits mutually exclusive IR and Raman v(TeO) bands. While little is known about the structure of this compound, the vibrational data indicate that it probably Controlled Hydrolysis of the Hexafluorides of Molybdenum, Tungsten, and Rhenium: Structure of Oxonium (ju-Fluoro)bis(tetrafluorooxotungstate(VI)

Lewis Acidic Behavior of MoOF4 towards the Alkali Metal Fluorides in Anhydrous Hydrogen Fluoride Solutions

“…It was observed that the K[Mo 2 O 2 F 9 ], Rb[Mo 2 O 2 F 9 ], and Cs[Mo 2 O 2 F 9 ] salts are isotypic to each other, so only the potassium salt will be discussed in detail. Additionally, these salts are also isotypic to the previously reported [H 3 O]W 2 O 2 F 9 salt …”

“…First, MoOF 4 was synthesized through the hydrolysis of MoF 6 by silicon dioxide in aHF, see Equations 4 and 5 . After pumping off the unreacted aHF and the SiF 4 formed during the reaction, the MoOF 4 product was stored in an inert atmosphere glovebox until further use.…”

“…First, MoOF 4 was synthesized through the hydrolysis of MoF 6 by silicon dioxide in aHF, see Equations 4 and 5. [23] After pumping off the unreacted aHF and the SiF 4 formed during the reaction, the MoOF 4 product was stored in an inert atmosphere glovebox until further use. Next, a 1:1 molar ratio of MoOF 4 and the respective alkali metal fluoride was reacted in an aHF solution to obtain the M[Mo 2 O 2 F 9 ] (M = Li-Cs) salts, see Equation 6.…”

Dinuclear oxofluorometallates as a new structural type of d 0 transition metal oxofluoride compound

“…Fluorine-bridging species [W 2 O 2 F 9 ] À (McFarlane et al, 1971;Buslaev, Kokunov, Bochkareva & Shoustorovich et al, 1972) (Casteel et al, 1998) were found in organic mediums, (CH 3 O) 2 SO, CH 3 CN. The controlled hydrolysis of hexafluorides of molybdenum, tungsten and rhenium also yielded the fluorine-bridged [M 2 O 2 F 9 ] À species (Hoskins et al, 1987). In all these species, the O atoms are trans to the F bridging atoms as in our cases (I)-(V).…”

Crystal structure of an ordered [WOF5]− salt: (1,10-phen-H)[WOF5] (1,10-phen = 1,10-phenanthroline)

“…In all cases, mutual cis arrangements of the oxido ligands are preferred (i.e., cis-[WO 2 F 4 ] 2À and fac-[WO 3 F 3 ] 3À ). A trans influence from the oxido ligands results in increased electron density on ISSN 2056-9890 the effected fluorido ligands, and it is these fluorido ligands that participate in fluorine bridging within multinuclear systems, such as in WOF 4 and in various [W 2 O 2 F 9 ] À salts with different counterions {[H 3 O] + (Hoskins et al, 1987); [WF 4 (2,2 0bipy) 2 ] 2+ (Arnaudet et al, 1992); [Os 3 (CO) 12 H] + (Crossman et al, 1996); [XeF 5 ] + (Bortolus et al, 2020); Li-Cs + (Stene et al, 2020)}, and in [W 2 O 4 F 6 ] 2À (Wollert et al, 1991).…”