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Bi nuclear copper ii complexes as mimics for type 3 coppers in metallo enzymes part 1 the importance of cooperative interactions between metals in the reversible multi electron transfer in bis 1 3 5 tri ketonato di copper ii complexes



Bi nuclear copper ii complexes as mimics for type 3 coppers in metallo enzymes part 1 the importance of cooperative interactions between metals in the reversible multi electron transfer in bis 1 3 5 tri ketonato di copper ii complexes



Journal of the American Chemical Society 100(20): 6367-6375



The electrochemistry of several bis(1,3,5-triketonato)dicopper(II) complexes that have magnetic and spectral properties similar to type 3 Cu in metalloenzymes was investigated. Experimentally, these complexes adhere to the usual criteria for reversibility, have diffusion constants typical of 2-electron transfer, have cyclic voltammographs with 42 mV peak separations, and give standard polarographic plots with 46 .+-. 3 mV slopes. The quantitative addition of 2 electrons/molecule is proven by controlled potential electrolysis. All of these facts are consistent with the 2-electron reversible reduction of the Cu(II), Cu(II) complex to a Cu(I), Cu(I) product in which the electrons are added sequentially at the same potential. The net result is a single-potential, 2-electron transfer. The importance of cooperative interactions between the metals, the magnetic interactions, the structural parameters and the substituent groups is discussed. The redox reactions of type 3 Cu probably involve 2-electron transfer. Therefore, the observed redox properties together with the magnetic and spectral properties make the bis(1,3,5-triketonato)Cu(II) complexes potential mimics for type 3 Cu in metalloenzymes.

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