Lacunary tungstotellurates(iv): [Te2W17O61]12−, [Te2W16O58(OH)2]14− and [Te2W18O62(OH)2]10−

Abstract

A simple procedure is reported for the isolation of the new lacunary tungstotellurate(IV) [Te(2)W(17)O(61)](12-) (1a) in multi-gram quantities, with (125)Te and (183)W NMR spectroscopy indicating retention of the solid state structure in solution. The structurally related polyanions [Te(2)W(16)O(58)(OH)(2)](14-) (2a) and [Te(2)W(18)O(62)(OH)(2)](10-) (2b) were also isolated.

Selective conversion of {Mo132} Keplerate ion into 4-electron reduced crown-capped Keggin derivative [Te5Mo15O57]8−. A key intermediate to single-phase M1 multielement MoVTeO light-alkanes oxidation catalyst

“…This latter could be assigned to the Te atom in the {TeMo 6 O 24 } crown moiety, far from the electronic delocalization pathway and observed in the usual range for a {TeO 3 } coordination type. 11 Typically, the observed moderate shielding at this Te nucleus (Dv = À63 ppm with respect to the uncoordinated {TeO 3 } group) could be due to its encapsulation within the {Mo 6 O 24 } crown. Finally, a variable-temperature 125 Te NMR experiment between 209-350 K revealed that the position of the high frequency resonance was strongly dependent upon the temperature (see ESIw).…”

Four Members of the Sandwich‐Type Polytungstophosphate Family Based on Pentalacunary [HPW7O28]8– Building Blocks

“…In contrast, 1a displays a new sandwich‐type POM. Moreover, the {HPW 7 O 28 } (Figure 2, a) moiety can be viewed as another configuration of the pentalacunary Keggin fragment, which is different from the {TeW 7 O 28 } ( C , Figure 2, b) and [AsMo 7 O 27 ] ( D , Figure 2, c) fragments evident in the [Te 2 W 16 O 58 (OH) 2 ] 14– , [Te 2 W 18 O 62 (OH) 2 ],10–12d and [MM′(As III ‐Mo 7 O 27 ) 2 ] 12/14– (MM′ = CuCu, CrCr, FeCr, FeFe)11b polyoxoanions, respectively. Fragment C is thought to originate from the trivacant Keggin‐type {TeW 9 } unit by omitting one edge‐shared {W 2 O 10 } unit in the equator, which leaves two edge‐shared {W 2 O 10 } units corner shared.…”

“…Interestingly, relative to the abundant amount of research on TM‐HPTs, the number of structurally characterized TM‐containing pentavacant Keggin polyoxomolybdates11 and polyoxotungstates12 is still rather limited. Hitherto, to the best of our knowledge, only four types of heptatungstate {XW 7 } (X = P,12a,12b As,12a V,12c Te12d) polyanions are known. In 2005, Kortz and co‐workers prepared the pioneering examples of ruthenium(II)‐supported heteropolyanions [HXW 7 O 28 Ru(dmso) 3 ] 6– (X = P, As), which are composed of a Ru(dmso) 3 group attached to an unprecedented heptatungstate fragment 12a.…”

“…Subsequently, Wu et al communicated the heptatungstovanadate analogue [HVW 7 O 28 Ru(dmso) 3 ] 6– in 2010 12c. The same year, the Boskovic group reported unfunctionalized POMs based on the Te‐containing lacunary Keggin ions [Te 2 W 16 O 58 (OH) 2 ] 14– and [Te 2 W 18 O 62 (OH) 2 ] 10– 12d. These two polyoxoanions contain a previously unreported lacunary Keggin building block [A‐α‐TeW 7 O 28 ] 10– .…”

Rare-Earth-Incorporated Tellurotungstate Hybrids Functionalized by 2-Picolinic Acid Ligands: Syntheses, Structures, and Properties

“…For example, in 2009, Kortz et al isolated two novel TT species [H 2 Te 4 W 20 O 80 ] 22– and [NaTeW 15 O 54 ] 13– by the one-pot self-assembly reaction of Na 2 WO 4 and TeO 2 in a pH 7.5 aqueous solution, where [H 2 Te 4 W 20 O 80 ] 22– comprises two [HTe 2 W 10 O 40 ] 11– fragments joined via Te–O–W bridges and [NaTeW 15 O 54 ] 13– consists of a triangular assembly by 15 edge- and corner-sharing WO 6 octahedra that are divided into three identical {W 5 } groups, surrounding a trigonal-pyramidal Te IV center residing in the central cavity and a capping sodium ion . Subsequently, Boskovic and co-workers reported the three dimeric TTs [Te 2 W 17 O 61 ] 12– , [Te 2 W 16 O 58 (OH) 2 ] 14– , and [Te 2 W 18 O 62 (OH) 2 ] 10– , which include previously unreported lacunary Keggin fragments [B-β-TeW 8 O 30 ] 8– and [A-α- TeW 7 O 28 ] 10– . Cronin et al prepared several nanoscale macrocyclic aggregates [W 28 Te 8 O 112 ] 24– , [W 28 Te 9 O 115 ] 26– , and [W 28 Te 10 O 118 ] 28– by a time-dependent synthetic approach in 2011, in which the tellurite anions can act as templates in [W 7 O 25 (TeO 3 )] 10– structural building units and linkers between them as well as pendant ligands in control of intercluster aggregation .…”