POM-FLPs: [MoIV3]_n-polyoxometalate bifunctional catalysis by [MoIV3]_n–O_m Lewis pairs frustrated by triangular Mo^IV–Mo^IV bonds

Abstract

The largest [Mo@Mo20]-1 and the first [Ge@Mo16Zn0.5Ge1.5]-2 incorporating group IV metals are added to the [MoIV3]n-POMs hybrid cluster family, which allows for the first systematic investigation into their reasonable syntheses, diversified molecular and electronic structures, and their influence on the catalytic hydrogenation performance of such POM-FLPs system.

Metal–metal bonds in polyoxometalate chemistry

“…109 The first polyanion was produced with the help of [Mo3O4(Hnta)3] 2− (where Hnta = nitrilotriacetic acid) precursor, 110 although in the follow-up studies [Mo3O2(O2CCH3)6(H2O)3] 2+ precursor was employed. 74 Some of the follow-up studies involve reports on [Sb III 3Mo IV 3Mo VI 15O55(OH)2(py)3] − , 111 [Mo@Mo IV 6Mo V 6Mo VI 9O54(OH)4(py)6] 4− , 112 and [Na@Mo IV 12Mo V 4Mo VI 3O43(OH)(py)12] (all in Figure 6). 113 These polyanions have peculiarities in terms of structure, and they have been in a great detail outlined in the primary literature.…”

“…From these results, the rearrangements of the metal−metal bonds in the super-reduced Keggin 106 appear plausible (vide supra). With the addition of different heterogroups (e.g., PO4 3− and GeO4 3− ) the group of Xu also discovered the formation of [Mo IV 3Mo VI 10Zn(PO4)4(OH)2O31py3] 2− , 113 and [Mo IV 6Mo VI 10Ge3O48py6], 112 which can be described as lacunary POMs incorporating triangular moieties.…”

Selective Oxidative Coupling of Amines Using Mesoporous MoOx Catalysts

“… BEs of Mo 3d from the literature have also been compared to assign the real oxidation state of the present measurement (Table S4). − The meso -MoO x -300 material is a mixture of +4, +5, and +6 oxidation states of molybdenum, with a majority of +6 oxidation states, as shown in Figure A. XPS data for synthesized molybdenum oxide show three doublet pairs (i.e., six synthetic peaks) and fit well to all the experimental Mo 3d spectra.…”

Ionothermal Synthesis of an Antimonomolybdate Cluster, [Sb8MoVI13MoV5O66]5–, and Its Catalytic Behavior to the Reduction of Nitrobenzene

“…The direct reduction of aromatic nitro compounds is one of the principal methods to obtain aromatic amines, and much effort has been devoted to developing efficient catalysts with cost-effectiveness for the reduction. − Reductions catalyzed by Lewis acid/base and ILs have been proven in previous works. − Very recently, Xu’s group employed mixed-valence POMo as the catalyst to reduce the aromatic nitro compound and receive an unexpected result of high catalytic performance. ,, In view of the structure made up of a Lewis base anion of a mixed-valence antimonomolybdate cluster and IL cations of EMIm, an excellent catalytic activity to the reduction should be anticipated for 1-Sb 8 Mo 18 .…”

“…45−47 Very recently, Xu's group employed mixed-valence POMo as the catalyst to reduce the aromatic nitro compound and receive an unexpected result of high catalytic performance. 29,48,49 In view of the structure made up of a Lewis base anion of a mixed-valence antimonomolybdate cluster and IL cations of EMIm, an excellent catalytic activity to the reduction should be anticipated for 1-Sb 8 Mo 18 .…”