Copper diketiminate complexes

A thallium(I) /3-diketiminate, [HC (Me)C(C6H3-2,6-Me2)N 2]Tl, and its use in the preparation of copper(I) complexes are reported. " No structural data are available on this compound. Thallium(I) complexes of 1,3-diphenyltriazenide and 1,5-di-/)-tolylpentaazadienes have been synthesized and structurally characterized. 

This compound was the first example of a three-coordinate complex of copper(II) outside a protein environment, and it is a precursor to other three-coordinate copper(II) complexes.1 The chloride ligand in this complex has been substituted with thiolate and phenolate ligands to give mimics of type 1 copper sites1,2 and of reduced galactose oxidase,3 respectively. Itoh and Tolman have examined the influence of diketiminate substitution pattern on the copper(II) chemistry.4... 

To contribute to an understanding of basic copper-dioxygen chemistry and to characterize species of possible relevance to D/3M and PHM, various model studies have been recently described. A side-on bound superoxo copper(H) complex was synthesized and characterized by Fujisawa, Kitajima, and co-workers by reacting the copper(l) complex of a substituted tris(pyrazolyl)borate (HB(3- Bu-5-iPrpz)s ) ligand with O2 at low temperature (Fig. 6) (68,69) Tolman and co-workers also reported a side-on peroxocopper(lll) complex with sterically hindered /3-diketiminate ligand (Dk R = Me or -Bu) (Fig. 6) (70). These complexes appear not to be reactive toward substrates, probably due to the steric bulk on the ligands that provide for complex stability and successful structural... 

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