Synthesis of heteropoly anions in aprotic solvents. Tungstorhenates(V),-(VI), and -(VII)

Functionalization of Heteropolyanions—Osmium and Rhenium Nitrido Derivatives of Keggin‐ and Dawson‐Type Polyoxotungstates: Synthesis, Characterization and Multinuclear (183W, 15N) NMR, EPR, IR, and UV/Vis Fingerprints

“…Synthesis : A great number of d n transition‐metal‐substituted POMs can be obtained from monovacant POMs, especially the Keggin‐ and Dawson‐type tungstophosphates. The method can be used for the preparation of oxo, for example, [α‐PW 11 O 39 {Re V O}] 4− 36 and [α‐PW 11 O 39 {Mo V O}] 4− ,37, 38 and organoimido [α‐PW 11 O 39 {Re V (NPh)}] 4− 22 derivatives. The method also applies to the synthesis of the nitrido‐functionalized POMs: it was first used to prepare [α‐PW 11 O 39 {TcN}] 4− 34 and has now been extended to the synthesis of [α‐PW 11 O 39 {Re VI N}] 4− , [α‐PW 11 O 39 {Os VI N}] 4− , [α 2 ‐P 2 W 17 O 61 {Os VI N}] 7− , and [α 1 ‐P 2 W 17 O 61 {Os VI N}] 7− .…”

Sorption of Pertechnetate by Salts of Molybdophosphoric Acid

“…10 40 ] 2 " complexes seems to be possible, because from the literature analogous complexes of Re(VII) and V(V) are known which have the composition of [PReW,, O 40 ] 2 " and [PVWj, 0 40 ] 4 respectively [10,11]. However, the existence of these complexes is limited to weakly acid solutions; in these solutions also heteropolyacids with a Mo : P-ratio <12 are obtained.…”

Quantum chemical studies on Re–Re quadruple-bonded Keggin-type polyoxometalate ([ (PW11O39)2]8−): Bonding feature and electron spectrum

“…This is the first example of multiple M-M bond involvement in POM chemistry, where the Re 6þ 2 dimeric core is coordinated to two lacunary Keggin-type POM ligands, [PW 11 O 39 ] 7À , which generate two transition-metal-substituted POM anions, [Re III {PW 11 O 39 }] 4À , that are directly linked together through a short, quadruple Re-Re bond of 2.27 Å (see Figure 1). The lacunary Keggin-type POM ligand, [PW 11 O 39 ] 7À , containing a defect formed by four oxygen donor atoms available for bonding to the transition metal, has been successfully used to stabilize transition metal ions in different oxidation states [28][29][30][31][32][33]. On the basis of a similar coordinated sphere relevant to porphyrin, this POM ligand can be viewed as an inorganic-porphyrin-like ligand.…”