Syntheses, Characterizations, Crystal Structures, and Protonation Reactions of Dinitrogen Chromium Complexes Supported with Triamidoamine Ligands.

A novel dinitrogen-dichromium complex, [{Cr(LBn)}2(µ-N2)] (1), has been prepared from reaction of CrCl3 with a lithiated triamidoamine ligand (Li3LBn) under dinitrogen. The X-ray crystal structure analysis of 1 revealed that it is composed of two independent dimeric Cr complexes bridged by N2 in the unit cell. The bridged N-N bond lengths (1.188(4) and 1.185(7) Å) were longer than the free dinitrogen molecule. The elongations of N-N bonds in 1 were also supported by the fact that the ν(N-N) stretching vibration at 1772 cm-1 observed in toluene is smaller than the free N2. Complex 1 was identified to be a 5-coordinated high spin Cr(IV) complex by Cr K-edge XANES measurement. The 1H NMR spectrum and temperature dependent magnetic susceptibility of 1 indicated that complex 1 is in the S = 1 ground state, in which two Cr(IV) ions and unpaired electron spins of the bridging N22- ligand are strongly antiferromagnetically coupled. Reaction of complex 1 with 2.3 equiv of Na or K gave chromium complexes with N2 between the Cr ion and the respective alkali metal ion, [{CrNa(LBn)(N2)(Et2O)}2] (2) and [{CrK(LBn)(N2)}4(Et2O)2] (3), respectively. Furthermore, the complexes 2 and 3 reacted with 15-crown-5 and 18-crown-6 to form the respective crown-ether adducts, [CrNa(LBn)(N2)(15-crown-5)] (4) and [CrK(LBn)(N2)(18-crown-6)] (5). The XANES measurements of complexes 2, 3, 4, and 5 revealed that they are high spin Cr(IV) complexes like complex 1. All complexes reacted with a reducing agent and a proton source to form NH3 and/or N2H4. The yields of these products in the presence of K+ were higher than those in the presence of Na+. The electronic structures and binding properties of 1, 2, 3, 4, and 5 were evaluated and discussed based on their DFT calculations.

The Steric Effect in Preparations of Vanadium(II)/(III) Dinitrogen Complexes of Triamidoamine Ligands Bearing Bulky Substituents.

The reactions of newly designed lithiated triamidoamines Li3LR (R = iPr, Pen, and Cy2) with VCl3(THF)3 under N2 yielded dinitrogen-divanadium complexes with a µ-N2 between vanadium atoms [{V(LR)}2(µ-N2)] (R = iPr (1) and Pen (2)) for the former two, while not dinitrogen-divanadium complexes but a mononuclear vanadium complex with a vacant site, [V(LCy2)] (R = Cy2 (3)), were obtained for the third ligand. The V-NN2 and N-N distances were 1.7655(18) and 1.219(4) Å for 1 and 1.7935(14) and 1.226(3) Å for 2, respectively. The ν(14N-14N) stretching vibrations of 1 and 2, as measured using resonance Raman spectroscopy, were detected at 1436 and 1412 cm-1, respectively. Complex 3 reacted with potassium metal in the presence of 18-crown-6-ether under N2 to give a hetero-dinuclear vanadium complex with µ-N2 between vanadium and potassium, [VK(LCy2)(µ-N2)(18-crown-6)] (4). The N-N distance and ν(14N-14N) stretching for 4 were 1.152(3) Å and 1818 cm-1, respectively, suggesting that 4 is more activated than complexes 1 and 2. The complexes 1, 2, 3, and 4 reacted with HOTf and K[C10H8] to give NH3 and N2H4. The yields of NH3 and N2H4 (per V atom) were 47 and 11% for 1, 38 and 16% for 2, 77 and 7% for 3, and 80 and 5% for 4, respectively, and 3 and 4, which have a ligand LCy2, showed higher reactivity than 1 and 2.

Dinitrogen Fixation by Vanadium Complexes with a Triamidoamine Ligand.

Dinitrogen-divanadium complexes with triamidoamine ligands, 1-3, were synthesized and characterized by resonance Raman, UV-vis, and NMR spectroscopy and elemental and X-ray structure analyses. X-ray structure analyses reveal that all three of the complexes have a dimeric structure with a µ-N2 ligand (N-N bond length 1.200-1.221 Å). Resonance Raman and NMR spectra of 1-3 in solution show that these complexes maintain a dimeric structure in benzene and toluene solutions. 15N NMR spectra of 1 and 3 have peaks assignable to µ-N2 ligands at 33.4 and 27.6 ppm, respectively, but 2 does not have a similar peak under the same conditions. In 51V NMR spectra, the peaks of vanadium ions were observed at -173.3, -143.8, and -240.2 ppm, respectively, which are in a higher magnetic field region in comparison to those of dinitrogen-divanadium complexes reported previously. The structure and electronic properties of 1 are supported by DFT calculations. Additionally, all complexes react with excess amounts of M[C10H8] (M = Na, K) and the proton sources HOTf, HCl, and [LutH]OTf (Lut = 2,6-dimethylpyridine) to produce ammonia without hydrazine. The ammonia produced was evaluated as an ammonium salt by 1H and 15N NMR spectroscopy. The yield of NH3 produced in the reaction of 1 with Na[C10H8] and HOTf under N2 was 151% (per V atom).

Metal-Free Homocoupling of Pyrene inside the Pores of Mesoporous Carbons via Electrochemical Oxidation: Application for Electrochemical Capacitors.

A pyrene dimer (PYD) is synthesized by electrochemical oxidation via homocoupling of pyrene (PY) inside the pores of MgO-templated mesoporous carbons without any metal catalysts or organic solvents. The resulting MgO-C/PYD hybrids can be used as high-performance aqueous electrochemical capacitor electrodes due to the reversible redox property of PYD and large contact area between the hybridized PYD and conductive carbon surfaces, which enable rapid charge transfer at the large contact interface. In our previous study, PY was considered to polymerize through electrochemical oxidation, and activated carbon with the pore sizes of ∼4 nm was used as a porous carbon substrate. In this study, the MgO-templated carbons have the average pore sizes of 5, 10, and 30 nm, and their large mesopore volumes can accommodate a large amount of PYD for enhancing the capacitance. To develop high-performance electrochemical capacitors, the dependence of the capacitance enhancement and the capacitance retention on the amount of PY and the pore sizes of MgO-templated carbons are studied. It is found that mesopores are necessary for fast charging/discharging, but the capacitance retention and capacitance enhancement decrease with increasing the mesopore sizes and the amount of PY due to the decreased utilization ratio of PY.

Enzyme immobilisation on poly-l-lysine-containing calcium phosphate particles for highly sensitive glucose detection.

High catalytic activities of enzymes are necessary for enzyme immobilising technology for the development of glucose sensors. The aim of this study is to synthesise two types of poly(l-lysine)-containing calcium phosphate particles (pLys-HAp) and to achieve the immobilisation of glucose oxidase (GOX) on them. The oxidation activity of GOX immobilised on these particles was more than 80% compared to that of native GOX (considered to be 100%). Additionally, the relative activity of GOX immobilised on poly-ε-lysine-containing HAp (ε-pLys-HAp) remained approximately 70% after ten cycles. Moreover, glucose detection was able to be performed in the linear range of 4-400 µM using GOX immobilised on pLys-HAp composites. In the direct electrochemistry measurement using the cyclic voltammetry (CV) method, a glassy carbon electrode (GCE) modified by ε-pLys-HAp was a good enzyme electrode and can be used for glucose detection with high sensitivity. From these results, poly(l-lysine)-containing HAp composites can be expected to be enzyme immobilisation agents with high stability and biosensors with high sensitivity.

Enhancement of activity and stability of the formaldehyde dehydrogenase by immobilizing onto phenyl-functionalized mesoporous silica.

Formaldehyde dehydrogenase (FDH, molecular size of 8.6 nm × 8.6 nm × 19.0 nm) was immobilized on seven types of mesoporous silica (MPS), whose pores were from 2.4 to 31.2 nm sized, and their catalytic activities were evaluated by oxidation of formaldehyde. Among MPSs, FDH immobilized on MPS-4 (pore size of 12.3 nm) showed the best catalytic activity. Enhancement of catalytic activity was obtained by immobilizing onto MPS, whose pore (mesopore) size was similar to the molecular size of FDH. In addition, FDH was immobilized on five types of organo-functionalized MPS-4. Results from assays of enzyme activity showed that FDH immobilized on phenyl-functionalized MPS-4 (MPS-4-Ph) had higher activity than FDH immobilized on non-functionalized one. Immobilized FDH on MPS-4-Ph was active for low formaldehyde concentration form 6.0 µM and more sensitive than conventional formaldehyde detectors. Stability of FDH activity was also evaluated under the various conditions, in which protein denaturation could occur by solvent treatment, such as methanol or sodium dodecyl sulfate. As a result, FDH stability was strongly improved by the immobilization on MPS materials. Further investigation using tryptophan fluorescence and circular dichroism (CD) indicated that the high-order structure of the FDH did not alter upon binding to the non-functionalized MPS surface. On the other hand, FDH immobilized on functionalized-MPS was changed by hydrophobic interaction or covalent binding. Consequently, substrate affinity was improved by the change in the structure of FDH and then the orientation of the active site.