Catalysis of “outer-phase” oxygen atom exchange reactions by encapsulated “inner-phase” water in {V₁₅Sb₆}-type polyoxovanadates

Abstract

A water molecule encapsulated inside water-soluble {V15Sb6} antimonato polyoxovanadate cages accelerates oxygen-exchange reactions in the cluster periphery.

New Water‐Soluble Cluster Compound {Zn(en)3}3[V15Sb6O42(H2O)]⋅ (Ethylenediamine)3⋅10 H2O as a Synthon for the Generation of Two New Antimonato Polyoxovanadates

“…This process results in overlapping isotope patterns for all peaks. [10] The corresponding reaction of the new compound II is clearlys lower and reaches ac onversion of 50 %o nly after 330 h. This indicatesasignificantly in- Compound II crystallizes in the chiral non-centrosymmetric monoclinic space group P2 1 ,w ith two formula units per unit cell (Table S1). Net exchange of aV Ou nit by an SbÀOÀSb unit has also been observedf or the well-studied Ni analogue I.…”

“…These clusteri ons contain an encapsulated water molecule, as also shown by X-ray crystal structure analysis (see below). [10] However,t he products obtainedb yp ost-functionalization of I and II differ in their clusters tructures. This process results in overlapping isotope patterns for all peaks.…”

Configurational Isomerism in Polyoxovanadates

“…Themost prominent fragmentation is the cleavage of the dimeric into monomeric ions,f ollowed by the loss of water and hydroxyl radicals as previously described for the in situ-formed {V 14 Sb 8 }c luster ( Figure S23). [4] Most interestingly,asecond fragmentation pathway is able to compete: ions,y ielding the dimeric [(N·H-OH)·Ni-(cyclen)] 2 3À complex ( Figure 4). As the first fragmentation pathway is clearly favored by the reduction of charge repulsion, the less intense yet characteristic loss of neutral species from the dimeric complex clearly points to aremarkable binding energy connecting the two a 1 *monomers in the gas phase.…”

“…[4,5] The addition of cyclen (1,4,7,10- This isomer is characterized by the inverted orientation (that is,pointing inwards) of one of its edge-sharing VO 5 pyramids,reducing the molecular symmetry to C 2v .Compound 2 features the first hetero-POV displaying configurational isomerism, and as the isomerization of the vanadyl moieties can occur at different positions, this Sb-POVisfurthermore subject to positional isomerism, [6] an aspect that may complicate synthesis and isolation of atargeted isomer. [4,5] The addition of cyclen (1,4,7,10- This isomer is characterized by the inverted orientation (that is,pointing inwards) of one of its edge-sharing VO 5 pyramids,reducing the molecular symmetry to C 2v .Compound 2 features the first hetero-POV displaying configurational isomerism, and as the isomerization of the vanadyl moieties can occur at different positions, this Sb-POVisfurthermore subject to positional isomerism, [6] an aspect that may complicate synthesis and isolation of atargeted isomer.…”

Unprecedented Connection Mode of [V16Sb4O42(H2O)]8– Cluster Anions by Mn2+ Centered Complexes: Solvothermal Synthesis and Properties of {[Mn(teta)]4V16Sb4O42(H2O}n·[(H2O)12]n

“…[9][10][11][12][13][14][15][16][17] The chemistry and structural diversity could be expanded by formation of inorganic-organic hybrid structures like observed in [V 14 [18] or in [{Co II (teta) 2 [19] While all these compounds were synthesized under solvothermal conditions applying Sb and V compounds as starting materials, further Sb-POVs could be prepared recently applying a water soluble Sb-POV. [20][21][22] In literature 34 Sb-POVs have been reported, of which 11 belong to the {V 14 16 } cluster is interconnected by a transition metal complex to form a chain, [9] while in all other {V 16 } anion based compounds cations and anions are isolated.…”