86847-79-2Relevant articles and documents
Preparations, Structures, and Properties of Copper(II) Complexes with a New Tripodal Tetradentate Ligand, N-(2-Pyridylmethyl)bis(6-pivalamido-2-pyridylmethyl)amine, and Reactivities of the Cu(I) Complex with Dioxygen
Harata, Manabu,Hasegawa, Koji,Jitsukawa, Koichiro,Masuda, Hideki,Einaga, Hisahiko
, p. 1031 - 1038 (1998)
Copper complexes of a tripodal tetradentate ligand, N-(2-pyridylmethyl)bis(6-pivalamido-2-pyridylmethyl)amine (Hbppa), have been prepared as a model of metal centers of mononuclear copper enzymes; their structures and properties have been examined together with those having several secondary ligands by electronic absorption, ESR and FAB mass spectral, cyclic voltammetric, and X-ray diffraction methods. The complexes, [Cu(Hbppa)](ClO4)2 and [Cu(Hbppa)(N3)]- ClO4·H2O, were obtained as single crystals, whose crystal structures revealed square-planar and trigonal-bipyramidal geometries, respectively. The electronic absorption and ESR spectra for the CuII(Hbppa)-X systems (X = no, Cl-, Br-, I-, N3-, and CH3COO-) allowed us to conclude that the complexes form several coordination geometries, such as square-planar, square-pyramidal, and trigonal-bipyramidal, depending upon the solvents (MeOH, MeCN). The redox potentials of [Cu(Hbppa)Cl]Cl in MeCN, THF, MeOH, and CH2Cl2 showed quasi-reversible CuI/CuII couples in the range of -0.056 - +0.085 V vs. Ag/AgCl at room temperature. The addition of dioxygen to the Cu(I)-Hbppa, which was prepared from [Cu(MeCN)4]PF6 and Hbppa (1:1) in EtCN at -78°C, resulted in a graduate absorption spectral change with two well-separated absorption maxima at 665 (ε= 162 M-1 cm-1) and 837 nm (ε = 305 M-1 cm-1) and an intense band at 375 nm (ε = 641 M-1 cm-1) as a shoulder. Simultaneous ESR experiments of the same complex solution exhibited a silent spectrum, indicating that the complex is diamagnetic. A similar electronic absorption spectral change was observed in MeOH with absorption peaks at 387 nm (ε = 843 M-1 cm-1), 640 (ε = 183 M-1 cm-1) and 828 (ε = 289 M-1 cm-1), although the ESR spectrum did not continue to be completely silent. Increasing the temperature of the solution up to room temperature demonstrated the formation of [Cu(Hbppa)(OH)]- species, whose X-ray structure was [Cu(Hbppa)(OH)]PF6·H2O. The reaction of the [Cu(Hbppa)]ClO4-sodium benzoylformate system with dioxygen in DMF resulted in production of carbon dioxide and benzoic acid, as analyzed by GC and HPLC.
Synthesis and Structure of a New Tripodal Polypyridine Copper(II) Complex That Enables to Recognize a Small Molecule
Harata, Manabu,Jitsukawa, Koichiro,Masuda, Hideki,Einaga, Hisahiko
, p. 61 - 62 (1995)
With a view to constructing an artificial metalloenzyme model complex which can recognize and capture a small molecule, a new tripodal ligand, tris(6-pivaloylamino-2-pyridylmethyl)amine, and its mononuclear copper(II) complex has been synthesized, and they were characterized by 1H-NMR and positive-ion FAB mass spectra, cyclic voltammetry and X-ray structure analysis.
Photoinduced Trifluoromethylation of Arenes and Heteroarenes Catalyzed by High-Valent Nickel Complexes
Deolka, Shubham,Govindarajan, Ramadoss,Khaskin, Eugene,Fayzullin, Robert R.,Roy, Michael C.,Khusnutdinova, Julia R.
supporting information, p. 24620 - 24629 (2021/10/08)
We describe a series of air-stable NiIII complexes supported by a simple, robust naphthyridine-based ligand. Access to the high-valent oxidation state is enabled by the CF3 ligands on the nickel, while the naphthyridine exhibits either a monodentate or bidentate coordination mode that depends on the oxidation state and sterics, and enables facile aerobic oxidation of NiII to NiIII. These NiIII complexes act as efficient catalysts for photoinduced C(sp2)?H bond trifluoromethylation reactions of (hetero)arenes using versatile synthetic protocols. This blue LED light-mediated catalytic protocol proceeds via a radical pathway and demonstrates potential in the late-stage functionalization of drug analogs.
Dioxygen-Derived Nonheme Mononuclear FeIII(OH) Complex and Its Reactivity with Carbon Radicals
Yadav, Vishal,Gordon, Jesse B.,Siegler, Maxime A.,Goldberg, David P.
supporting information, p. 10148 - 10153 (2019/07/05)
A new tetradentate, monoanionic, mixed N/O donor ligand (BNPAPh2O-) with second coordination sphere H-bonding groups has been synthesized for stabilization of a terminal FeIII(OH) complex. The complex FeII(BNPAPh2O)(OTf) (1) reacts with O2 to give a mononuclear terminal FeIII(OH) complex, FeIII(OH)(BNPAPh2O)(OTf) (2), both of which were characterized by X-ray diffraction, electrospray ionization mass spectrometry, UV-vis, 1H and 19F nuclear magnetic resonance, 57Fe M?ssbauer, and electron paramagnetic resonance spectroscopies. Treatment of 2 with carbon radicals (Ar3C·) gives Ar3COH and the FeII complex 1, in direct analogy with the elusive radical "rebound" process proposed for nonheme iron enzymes.
A switch type zinc ion fluorescent probe and its preparation method and application
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Paragraph 0048-0051, (2019/02/02)
The invention provides a open-closed type zinc ion fluorescent probe and a preparation method and an application thereof; the open-closed type zinc ion fluorescent probe has the structure described in the specification. The probe takes a rhodamine dye as
