Lindqvist-Type Oxo-Nitrosyl Complexes. Syntheses, Vibrational, Multinuclear Magnetic Resonance (14N, 17O, 95Mo, and 183W), and Electrochemical Studies of [M5O18{M'(NO)}]3- anions (M, M' = Mo, W)

DFT Calculations of the 183W NMR Chemical Shifts in Reduced Polyoxotungstates

“…www.eurjic.org [16] or the influence of the passing electron density. However, the oxygen atoms of this type have a higher shift [25] in CH 3 OTiW 5 O 18 3-, where no delocalization occurs.…”

“…Formally, NO has a charge of 1+. [16] The oxidized anion has no counterpart and for purposes of comparison the Lindqvist anion is used. Although the X-ray geometry of this anion was not determined because the lattice cells are very similar, the atomic coordinates were inferred from the general description of the related anion Mo 5 O 18 MoNO 3-and by comparison with the Lindqvist molybdate and tungstate anions.…”

“…[13] Several cases, however, should be considered separately. In the nitrosyl complexes W 5 O 18 W II NO 3-with the Lindqvist-type structure, [16] PW 11 W II NO 40 8-, and the corresponding Ru complexes with the Keggin structure, [17][18][19] the electron density of the cation introduced delocalizes onto the neighboring tungsten atoms.…”

Lindqvist‐Type (Aryldiazenido)polyoxomolybdates − Synthesis, and Structural and Spectroscopic Characterization of Compounds of the Type (nBu4N)3[Mo6O18(N2Ar)]

“…From electronic considerations, these ligands fall into two categories, the first being the π-donor imido and nitrido ligands, RN 2Ϫ and N 3Ϫ , respectively, which can substitute for oxo ligands without a change in the oxidation state of the metal atom Ϫ although reduction of Mo VI to Mo V is sometimes observed in the course of the reactions of polyoxomolybdates with precursors of imido and nitrido ligands Ϫ and the second being the π-acceptor nitrosyl ligand, which cannot bind to a d 0 metal centre. Consequently, (nitrosyl)polyoxometalates always contain reduced centres, for example, d 4 (M II ) and d 6 (M 0 ) in {M(NO)} 3ϩ [3Ϫ7] and {M(NO) 2 } 2ϩ [11] units (M ϭ Mo, W), respectively. Because of the analogy between nitrosyl and diazenido ligands, [12] there should be structurally related pairs of nitrosyl and diazenido derivatives of polyoxometalates, which might be obtained Ϫ at least in principle Ϫ through analogous reactions between hydroxylamine or monosubstituted hydrazines and polyoxomolybdates.…”

Electroactive Benzothiazole Hydrazones and Their [Mo6O19]2− Derivatives: Promising Building Blocks for Conducting Molecular Materials

“…L] nÀ in which L is a nitrogenous ligand. Following the pioneering investigations by Zubieta and co-workers, [46] this family of polyanions has been extended by Errington, Maatta, Proust, Peng and Wei groups [32] and now includes nitrosyl, [47][48][49] hydrazido, [50] diazenido [46,[51][52] nitrido [50] and imido [53][54][55][56][57][58] derivatives. One diazoalkane derivative has been also reported by Maatta and coworkers.…”