Functionalized heteropolyanions: high-valent metal nitrido fragments incorporated into a Keggin polyoxometalate structureElectronic supplementary information (ESI) available: general synthetic and characterization details. See http://www.rsc.org/suppdata/cc/b2/b209173a/

Abstract

Three examples of nitrido-functionalized polyoxometalate species are reported, namely (n-Bu4N)4[PW11O39(OsN)] (1), (n-Bu4N)4[PW11O39(ReN)] (2), and (n-Bu4N)3[PW11O39(ReN)] (3), which feature the incorporation of [OsVI identical to N]3+, [ReVI identical to N]3+ and [ReVII identical to N]4+ fragments, respectively, into the framework of a Keggin-type heteropolyanion.

Vicinal Dinitridoruthenium‐Substituted Polyoxometalates γ‐[XW10O38{RuN}2]6− (X=Si or Ge)

“…The direct reaction between the divacant derivative K 8 [g-XW 10 O 36 ] (X= Si, Ge) and two equivalents of the metal-nitrido precursor,…”

“…The difficulty here is threefold. The first issue is that K 8 [g-XW 10 O 36 ] (X= Si, Ge) has a relatively narrow pH range of stability. Below pH 4 (this value depends on the concentration of the polyoxometalate as well as the nature of the cations), it decomposes into a ensemble of compounds ultimately giving a-[XW 11 O 39 ] 8À or a-[XW 12 O 40 ] 4À , depending on the pH.…”

“…Below pH 4 (this value depends on the concentration of the polyoxometalate as well as the nature of the cations), it decomposes into a ensemble of compounds ultimately giving a-[XW 11 O 39 ] 8À or a-[XW 12 O 40 ] 4À , depending on the pH. [50] Owing to the intrinsic acidity of the {Ru VI N} 3 + fragment, the natural pH of a solution of K 8 [g-XW 10 O 36 ] (X= Si, Ge) and Cs 2 A C H T U N G T R E N N U N G [Ru VI NCl 5 ] is below 3, thus to some extent rearrangement of the polyoxometalate is expected. Attempts to crystallize other ruthenium-containing species from the still dark mother solution after filtration of 1 a were not successful.…”

“…This, in addition to their ability to stabilize high oxidation state cations, makes polyoxometalates the species of choice for effective and stable oxygenatom transfer catalysts. [8,9] Because the nitrido ligand, N 3À , is isoelectronic with the oxo ligand O 2À , polyoxometalates have also proved their ability to stabilize the terminal metal-nitrido function with metals as varied as osmium, rhenium, [10][11][12][13] technetium, [14] ruthenium, [15,16] chromium, [17] and manganese. [18] Nuclearity is a very important parameter in the chemistry of oxo complexes.…”

“…Several of the oxidases have active sites comprising clusters of d-electron transition-metal cations bridged by chalcogenide anions. Some of the most studied of these are the Mn 4 O 4 Ca cluster of the oxygen-evolving center (OEC) in Photosystem II, [19,20] the Fe 2 site of methane monooxygenase, and the FeCu core of cytochrome c ox-Abstract: Reaction of the divacant polyoxometalate K 8 [g-XW 10 O 36 ] (X= Si, Ge) with two equivalents of the metal-nitrido precursor Cs 2 tively. EXAFS studies confirmed the key structural assignments from X-ray crystallography.…”