Synthesis, Characterization, and Efficient Catalytic Activities of a Nickel(II) Porphyrin: Remarkable Solvent and Substrate Effects on Participation of Multiple Active Oxidants.

A new nickel(II) porphyrin complex, [NiII (porp)] (1), has been synthesized and characterized by 1 H NMR, 13 C NMR and mass spectrometry analysis. This NiII porphyrin complex 1 quantitatively catalyzed the epoxidation reaction of a wide range of olefins with meta-chloroperoxybenzoic acid (m-CPBA) under mild conditions. Reactivity and Hammett studies, H218 O-exchange experiments, and the use of PPAA (peroxyphenylacetic acid) as a mechanistic probe suggested that participation of multiple active oxidants NiII -OOC(O)R 2, NiIV -Oxo 3, and NiIII -Oxo 4 within olefin epoxidation reactions by the nickel porphyrin complex is markedly affected by solvent polarity, concentration, and type of substrate. In aprotic solvent systems, such as toluene, CH2 Cl2 , and CH3 CN, multiple oxidants, NiII -(O)R 2, NiIV -Oxo 3, and NiIII -Oxo 4, operate simultaneously as the key active intermediates responsible for epoxidation reactions of easy-to-oxidize substrate cyclohexene, whereas NiIV -Oxo 3 and NiIII -Oxo 4 species become the common reactive oxidant for the difficult-to-oxidize substrate 1-octene. In a protic solvent system, a mixture of CH3 CN and H2 O (95:5), the NiII -OOC(O)R 2 undergoes heterolytic or homolytic O-O bond cleavage to afford NiIV -Oxo 3 and NiIII -Oxo 4 species by general acid catalysis prior to direct interaction between 2 and olefin, regardless of the type of substrate. In this case, only NiIV -Oxo 3 and NiIII -Oxo 4 species were the common reactive oxidant responsible for olefin epoxidation reactions.

Three-dimensional Zinc(II) and cadmium(II) coordination frameworks with N,N,N',N'-tetrakis(pyridin-4-yl)methanediamine: structure, photoluminescence, and catalysis.

Coordination polymer networks, i.e., [Zn(tpmd)(H2O)](NO3)2·7H2O (1) and [Cd(tpmd)(H2O)2](NO3)2·4H2O·4CH3OH (2), were assembled from M(II)(NO3)2 hydrates (M = Zn, Cd) and N,N,N',N'-tetrakis(pyridin-4-yl)methanediamine (tpmd) in CH3OH and characterized. 1 and 2 feature three-dimensional networks formed by coordination of the metal ions to the tpmd ligands. 1 exhibits a strong blue emission at ∼397 nm, while 2 shows strong emission at ∼361 nm. 1 is a more efficient catalyst for the transesterification of various esters than 2.

A discrete {Co4(µ3-OH)4}(4+) cluster with an oxygen-rich coordination environment as a catalyst for the epoxidation of various olefins.

Using the sterically hindered terphenyl-based carboxylate, the tetrameric Co(ii) complex [Co4(µ3-OH)4(µ-O2CAr(4F-Ph))2(µ-OTf)2(Py)4] () with an asymmetric cubane-type core has been synthesized and fully characterized by X-ray diffraction, UV-vis spectroscopy, and electron paramagnetic resonance spectroscopy. Interestingly, the cubane-type cobalt cluster with 3-chloroperoxybenzoic acid as the oxidant was found to be very effective in the epoxidation of a variety of olefins, including terminal olefins which are more challenging targeting substrates. Moreover, this catalytic system showed a fast reaction rate and high epoxide yields under mild conditions. Based on product analysis and Hammett studies, the use of peroxyphenylacetic acid as a mechanistic probe, H2(18)O-exchange experiments, and EPR studies, it has been proposed that multiple reactive cobalt-oxo species Co(V)[double bond, length as m-dash]O and Co(IV)[double bond, length as m-dash]O were involved in the olefin epoxidation.

Catalysis and molecular magnetism of dinuclear iron(III) complexes with N-(2-pyridylmethyl)-iminodiethanol/-ate.

The reaction of N-(2-pyridylmethyl)iminodiethanol (H2pmide) and Fe(NO3)3·9H2O in MeOH led to the formation of a dimeric iron(III) complex, [(Hpmide)Fe(NO3)]2(NO3)2·2CH3OH (1). Its anion-exchanged form, [(pmide)Fe(N3)]2 (2), was prepared by the reaction of 1and NaN3 in MeOH, during which the Hpmide ligand of 1 was also deprotonated. These compounds were investigated by single crystal X-ray diffraction and magnetochemistry. In complex 1, one iron(III) ion was bonded with a mono-deprotonated Hpmide ligand and a nitrate ion. The two iron(III) ions within the dinuclear unit were connected by two ethoxy groups with an inversion center. In 2, one iron(III) ion was coordinated with a deprotonated pmide ligand and an azide ion. The Fe(pmide)(N3) unit was related by symmetry through an inversion center. Both 1 and 2 efficiently catalyzed the oxidation of a variety of alcohols under mild conditions. The oxidation mechanism was proposed to involve an Fe(IV)=O intermediate as the major reactive species and an Fe(V)=O intermediate as a minor oxidant. Evidence for this proposal was derived from reactivity and Hammett studies, KIE (kH/kD) values, and the use of MPPH (2-methyl-1-phenylprop-2-yl hydroperoxide) as a mechanistic probe. Both compounds had significant antiferromagnetic interactions between the iron(III) ions via the oxygen atoms. 1 showed a strong antiferromagnetic interaction within the Fe(III) dimer, while 2 had a weak antiferromagnetic coupling within the Fe(III) dimer.

CO2 selective dynamic two-dimensional Zn(II) coordination polymer.

A CO2 selective dynamic two-dimensional (2D) MOF system, [Zn(glu)(µ-bpe)]·2H2O (·2H2O) (glu = glutarate, bpe = 1,2-bis(4-pyridyl)ethylene), is prepared. Based on variable temperature PXRD patterns, I·2H2O exhibits a structural transformation of the framework upon desolvation. Various gas sorption analyses at low temperatures reveal that solvent-free I selectively adsorbs CO2 over N2, H2, and CH4. Stepped CO2 isotherms for solvent-free I with a large hysteresis between adsorption and desorption branches at 196 K indicate that I is a dynamic framework. Moreover, I·2H2O shows efficient heterogeneous catalytic reactivity for transesterification of various esters. The catalyst can be recycled multiple times without losing its original activity.

Toxicological investigation of radioactive uranium in seawater.

Trace uranium detection measurement was performed using DNA immobilized on a graphite pencil electrode (DGE). The developed probe was connected to the portable handheld voltammetric systems used for seawater analysis. The sensitive voltammogram was obtained within only 30 s accumulation time, and the anodic stripping working range was attained at 100~800 µg/l U and 10~50 µg/l. The statistic relative standard deviation of 30.0 mg/l with the 15(th) stripping was 0.2115. Here, toxicological and analytical application was performed in the seawater survey in a contaminated power plant controlling water. The results were found to be applicable for real-time toxicological assay for trace control.

Bifunctional 3D Cu-MOFs containing glutarates and bipyridyl ligands: selective CO2 sorption and heterogeneous catalysis.

We report bifunctional three-dimensional (3D) Cu-MOFs with high selectivity of CO(2) over N(2) and H(2) as well as high catalytic activity for transesterification of esters. The Cu-MOFs containing Cu(2) dinuclear units connected by glutarates and bipyridyl ligands are formulated as [{Cu(2)(Glu)(2)(µ-bpa)}·(CH(3)CN)](n) (1) and [{Cu(2)(Glu)(2)(µ-bpp)}·(C(3)H(6)O)](n) (2) (Glu = glutarate, bpa = 1,2-bis(4-pyridyl)ethane, bpp = 1,3-bis(4-pyridyl)propane). These two new bifunctional 3D Cu-MOFs possess very similar pore shape with different pore dimensions. Their gas sorption behaviors were investigated by using CO(2), N(2) and H(2) at suitable temperatures. Both MOFs exhibited good CO(2) selectivity over N(2) and H(2). MOF 1 having a smaller pore dimension exhibited much higher CO(2) adsorption enthalpy than MOF 2 having a larger pore dimension. However, MOF 2 exhibited more enhanced CO(2) uptake ability than MOF 1. A subtle variation of pore dimension indeed influenced the CO(2) uptake ability somewhat significantly especially at higher temperatures such as 273 K and 298 K. Heterogeneous catalytic activities of the MOFs were also investigated in detail. Only MOF 1 appeared to be an efficient, mild, and easily recyclable heterogeneous catalyst for the transesterification of esters and constitutes a promising class of heterogeneous catalysts that allowed reuse without a significant loss of activity through twenty runs with ester.