Functionalized Heteropolyanions: High‐Valent Metal Nitrido Fragments Incorporated into a Keggin Polyoxometalate Structure.

Abstract

Osmium Osmium I 8100 Functionalized Heteropolyanions: High-Valent Metal Nitrido Fragments Incorporated into a Keggin Polyoxometalate Structure. -Three new nitrido-functionalized polyoxotungstates are synthesized which feature the incorporation of [Os VI ≡N] 3+ (III), [Re VI ≡N] 3+ (V), and [Re VII ≡N] 4+ fragments into the framework of a Keggin-type heteropolyanion. Compound (III) is characterized by 15 N, 31 P, and 183 W NMR and for (V) results obtained by EPR spectroscopy (confirming the paramagnetic character), cyclic voltammetry, and single crystal XRD (cubic, space group Im3m) are briefly reported. -(KWEN, H.; TOMLINSON, S.; MAATTA*, E. A.; DABLEMONT, C.; THOUVENOT, R.; PROUST, A.; GOUZERH, P.; Chem.

A DFT Study on the Electronic and Redox Properties of [PW11O39(ReN)]n–(n = 3, 4, 5) and [PW11O39(OsN)]2–

“…At the same time, Re and Os link to the nitrogen atom instead of the terminal oxygen atom (O t ). Figure 1 shows the optimized structure of PW 11 ReN, and other structures in this article are all similar to it. Some selected bond lengths are listed in Table 1.…”

“…[10] Three nitrido-functionalized polyoxometalate species, (nBu 4 N) 4 4+ fragments into the framework of a Keggin-type heteropolyanion were reported by Maatta. [11] It is the first time that rhenium-and osmiumnitrido were inserted into the polyoxometalate. [12][13][14][15][16] density functional theory (DFT), which has been proven to be a significant tool for understanding and rationalizing the electronic and magnetic properties of polyanions, [17][18][19][20][21][22][23][24][25][26] was employed to pursue the questions mentioned above.…”

New Vistas for Functionalized Polyoxometalates

“…Our first report 6 introduced both rhenium-and osmiumnitrido derivatives of the Keggin POM, i.e. [PW 11 2-whose structures as determined by single-crystal X-ray diffraction are shown below.…”

“…4,7 The prototype building block in this work is our styrylimido POM [Mo 6 O 18 (N-C 6 H 4 CH=CH 2 )] 2-whose structure is shown at right. Our initial synthesis of co-polymers with styrenic monomers has now been extended to include co-polymers of various acrylic materials.…”

“…We are exploring the potential of the styrylimido POM [Mo 6 O 18 (N-C 6 H 4 CH=CH 2 )] 2-as a platform for introducing additional functionality via metathetical exchanges at its vinyl group using Schrock and Grubbs catalysts. This styrylimido POM is especially promising for such reactions since it is accessible in high yield and its [Mo N] linkage is particularly robust.…”