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An acyclic diimine ligand, H4L1, formed in methanol from the condensation of 1,4-diformyl-2,3-dihydroxybenzene (1) with two equivalents of 2-aminoethanol, was reacted with two equivalents of solid zinc(II) acetate dihydrate. Diffusion of diethyl ether into the reaction solution yielded a mixture of orange crystals of an octanuclear complex, [ZnII8(H2L1)4(OAc)8] (2), and red crystals of a hendecanuclear complex, [ZnII11(H2L1)6(OAc)6(O)2] (3). 相似文献
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《Journal of Coordination Chemistry》2012,65(14):2415-2431
The synthesis, structure, and ligand substitution mechanism of a new five-coordinate trigonal-bipyramidal copper(II) complex, [CuII(py tBuMe2N3)Cl2] (1), with a sterically constrained py tBuMe2N3 chelate ligand, py tBuMe2N3?=?2,6-bis-(ketimino)pyridyl, are reported. The kinetics and mechanism of chloride substitution by thiourea, as a function of nucleophile concentration, temperature, and pressure, were studied in detail and compared with an earlier study reported for the analogous complex [CuII(py tBuN3)Cl2] (2) [py tBuN3?=?2,6-bis-(aldimino)pyridyl]. Catalysis of the oxidation of 3,5-di-tert-butylcatechol to 3,5-di-tert-butylquinone by 1 and 2 was studied. Correlations between the reactivity, chloride substitution behavior, and reduction potentials of both complexes were made. These show that the rate of oxidation is independent of the rate of chloride substitution, indicating that the substitution of chloride by catechol as substrate occurs in a fast step. Spectral data show a non-linear relationship between the ability of the complexes to oxidize 3,5-DTBC and the Lewis acidity of their copper(II) centers. Electrochemical data demonstrate that the most effective complex 1 has a E 0 value that approaches the E 0 value of the natural tyrosinase enzyme. 相似文献
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《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2018,130(15):4054-4058
The first catalytic inverse hydroboration of imines with N‐heterocyclic carbene (NHC) boranes has been realized by means of cooperative organocatalysis and photocatalysis. This catalytic combination provides a promising platform for promoting NHC‐boryl radical chemistry under sustainable and radical‐initiator‐free conditions. The highly important functional‐group compatibility and possible application in late‐stage hydroborations represent an important step forward to an enhanced α‐amino organoboron library. 相似文献