M(C6H16N3)2(VO3)4 as heterogeneous catalysts. Study of three new hybrid vanadates of cobalt(ii), nickel(ii) and copper(ii) with 1-(2-aminoethyl)piperazonium

Abstract

Three new hybrid vanadates have been synthesized under hydrothermal conditions with the formula M(C 6 H 16 N 3 ) 2 (VO 3 ) 4 , where M= Co(II), Ni(II) and Cu(II). The structural analyses show that the phases are isostructural and crystallize in the monoclinic space group P2 1 /c. These compounds show a two-10 dimensional crystal structure, with sheets composed of [VO 3 ]  n n chains and metal centres octahedrically coordinated, chelated by two 1(2-aminoethyl)pyperazonium ligands. The thermal study reveals that copper containing phase is less stable than cobalt and nickel containing ones. The IR spectra of the three phases are very similar, with little differences in the inorganic bond region of the copper containing phase. The UV-visible spectra show that the cobalt(II) and the nickel(II) are in slightly distorted 15 octahedral environments. The catalytic tests show that the phases act as heterogeneous catalysts for the selective oxidization of alkyl aryl sulfides, with both H 2 O 2 and tert-butylhydroperoxide as oxidizing agents. The influence of the steric hindrance in the kinetic profile had been studied. The catalytic reactions induce the partial amorphization of the phases.

Syntheses, structures and properties of two 2-D layered hybrid organic–inorganic materials based on different V4O12building units

“…1). Each Zn II center is connected with three O atoms from two {V 4 20 and M(C 6 H 16 N 3 ) 2 (VO 3 ) 4 (M = Co, Ni, Cu), 21 the V-O chain in compound 1 is sine wave-like which is more tortile than reported before.…”

“…The bond lengths of V-O range from 1.598(3) to 1.828(3) Å and the O-V-O angles range from 106.42(10)°to 112.07(15)°(Table S1a †), which are consistent with previously reported vanadates. [19][20][21] As shown in Fig. 3 chains in the [100] direction.…”

Double role of metalloporphyrins in catalytic bioinspired supramolecular metal–organic frameworks (SMOFs)

“…The reaction conditions were initially set using benzyl alcohol as a model substrate. Based on our previous experience (Fidalgo-Marijuan et al, 2015;Larrea et al, 2011), the reactions were carried out using tert-butyl hydroperoxide (TBHP) as the oxidizing agent in acetonitrile. Using 5% catalyst and 1.5 equivalents of TBHP in 2 ml of solvent at 343 K, total conversions of 50% for 1, 73% for 2 and 71% for 3 were achieved after 7 h of reaction.…”

Trapping ionic dimers of dinuclear peroxido mandelato complexes of vanadium(V) into cavities constructed from Δ- and Λ-[Ni(phenanthroline)3]2+ cations: a precursor to Ni(VO3)2

“…Nickel-vanadium hybrid compounds have also been investigated, e.g. as heterogenous catalysts [4], photocatalysts [5] or magnetic materials [6]. Special interest is focused on nickel vanadates that may be used as anode materials for lithium-ion batteries.…”