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Creators/Authors contains: "Na, Hanah"

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  1. Abstract

    Significant progress has been made in the bioinorganic modeling of the paramagnetic states believed to be involved in the hydrogen redox chemistry catalyzed by [NiFe] hydrogenase. However, the characterization and isolation of intermediates involved in mononuclear Ni electrocatalysts which are reported to operate through a NiI/IIIcycle have largely remained elusive. Herein, we report a NiIIcomplex (NCHS2)Ni(OTf)2, where NCHS2 is 3,7-dithia-1(2,6)-pyridina-5(1,3)-benzenacyclooctaphane, that is an efficient electrocatalyst for the hydrogen evolution reaction (HER) with turnover frequencies of ~3,000 s−1and a overpotential of 670 mV in the presence of trifluoroacetic acid. This electrocatalyst follows a hitherto unobserved HER mechanism involving C-H activation, which manifests as an inverse kinetic isotope effect for the overall hydrogen evolution reaction, and NiI/NiIIIintermediates, which have been characterized by EPR spectroscopy. We further validate the possibility of the involvement of NiIIIintermediates by the independent synthesis and characterization of organometallic NiIIIcomplexes.

     
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  2. Abstract

    Photoredox nickel catalysis has emerged as a powerful strategy for cross-coupling reactions. Although the involvement of paramagnetic Ni(I)/Ni(III) species as active intermediates in the catalytic cycle has been proposed, a thorough spectroscopic investigation of these species is lacking. Herein, we report the tridentate pyridinophane ligandsRN3 that allow for detailed mechanistic studies of the photocatalytic C–O coupling reaction. The derived (RN3)Ni complexes are active catalysts under mild conditions and without an additional photocatalyst. We also provide direct evidence for the key steps involving paramagnetic Ni species in the proposed catalytic cycle: the oxidative addition of an aryl halide to a Ni(I) species, the ligand exchange/transmetalation at a Ni(III) center, and the C–O reductive elimination from a Ni(III) species. Overall, the present work suggests theRN3 ligands are a practical platform for mechanistic studies of Ni-catalyzed reactions and for the development of new catalytic applications.

     
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  3. A bioinspired (N2S2)Ni( ii ) electrocatalyst is reported that produces H 2 from CF 3 CO 2 H with a turnover frequency (TOF) of ∼1250 s −1 at low acid concentration (<0.043 M) in MeCN. A mechanism for the H 2 production by this electrocatalyst is proposed and its activity is benchmarked against those of other reported molecular Ni H 2 evolution electrocatalysts. The involvement of a hemilabile pyridyl group of the N2S2 ligand is proposed to mimic the role of a cysteine residue involved in the biological proton reduction performed by [NiFe] hydrogenases. 
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  4. null (Ed.)
    Herein we report the isolation, characterization, and photoreactivity of a stable Ni III dichloride complex supported by a tetradentate pyridinophane N-donor ligand. Upon irradiation, this complex undergoes an efficient photoreductive chlorine elimination reaction, both in solution and the solid-state. Subsequently, the Ni III Cl 2 species can be regenerated via a reaction with PhICl 2 . 
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  5. Cyclometalated iridium complexes have emerged as top-performing emitters in organic light-emitting diodes (OLEDs) and other optoelectronic devices. A persistent challenge has been the development of cyclometalated iridium complexes with deep blue luminescence that have the requisite color purity, efficiency, and stability to function in color displays. In this work we report a new class of cyclometalated iridium complexes with saturated blue luminescence. These complexes have the general structure Ir(C^C: NHC ) 2 (C^C: ADC ), where C^C: NHC is an N-heterocyclic carbene (NHC) derived cyclometalating ligand and C^C: ADC is a different type of cyclometalating ligand featuring an acyclic diaminocarbene (ADC). The complexes are prepared by a cascade reaction that involves nucleophilic addition of propylamine to an isocyanide precursor followed by base-assisted cyclometalation of the ADC intermediate. All three emit deep blue light with good quantum efficiencies ( Φ PL = 0.13–0.48) and color profiles very close to the ideal primary blue standards for color displays. 
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