The three-dimensional configuration of the ester heterocycle is basically the same as that of the carbocycle. Compound: Nickel(II) chloride ethylene glycol dimethyl ether complex(SMILESS: COCCOC.Cl[Ni]Cl,cas:29046-78-4) is researched.Safety of 4-(Pyridin-2-yl)benzoic acid. The article 《3d-d excited states of Ni(II) complexes relevant to photoredox catalysis: spectroscopic identification and mechanistic implications》 in relation to this compound, is published in Journal of the American Chemical Society. Let’s take a look at the latest research on this compound (cas:29046-78-4).
Synthetic organic chem. has seen major advances due to the merger of nickel and photoredox catalysis. A growing number of Ni-photoredox reactions are proposed to involve generation of excited nickel species, sometimes even in the absence of a photoredox catalyst. To gain insights about these excited states, two of our groups previously studied the photophysics of Ni(t-Bubpy)(o-Tol)Cl, which is representative of proposed intermediates in many Ni-photoredox reactions. This complex was found to have a long-lived excited state (τ = 4 ns), which was computationally assigned as a metal-to-ligand charge transfer (MLCT) state with an energy of 1.6 eV (38 kcal/mol). This work evaluates the computational assignment exptl. using a series of related complexes. Ultrafast UV-Vis and mid-IR transient absorption data suggest that a MLCT state is generated initially upon excitation but decays to a long-lived state that is 3d-d rather than 3MLCT in character. Dynamic cis,trans-isomerization of the square planar complexes was observed in the dark using 1H NMR techniques, supporting that this 3d-d state is tetrahedral and accessible at ambient temperature Through a combination of transient absorption and NMR studies, the 3d-d state was determined to lie ∼0.5 eV (12 kcal/mol) above the ground state. Because the 3d-d state features a weak Ni-aryl bond, the excited Ni(II) complexes can undergo Ni homolysis to generate aryl radicals and Ni(I), both of which are supported exptl. Thus, photoinduced Ni-aryl homolysis offers a novel mechanism of initiating catalysis by Ni(I).
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Reference:
Indole alkaloid derivatives as building blocks of natural products from Bacillus thuringiensis and Bacillus velezensis and their antibacterial and antifungal activity study,
Preparation of Indole Containing Building Blocks for the Regiospecific Construction of Indole Appended Pyrazoles and Pyrroles