Synthesis and studies of Cu(II)-thiolato complexes: bioinorganic perspectives

A New Type 2 Copper Cysteinate Azurin

“…1A) and is characteristic of a type 2 copper site. It can be assigned as a RS Ϫ Ϫ Cu(II) 3 * band (15)(16)(17)(18). These features are strikingly different from the spectroscopic characteristics of Cu-H117G azurin mentioned above (Fig.…”

“…The first step is very fast: under pseudo-first order conditions an intermediate is formed within 10 ms with an absorption maximum at 385 nm, indicative of a RS Ϫ Ϫ Cu(II) 3 * band in a Cu(II)-thiolate center with a tetragonal geometry (15)(16)(17). The formation of such an intermediate has been observed during the incorporation of copper in a Cu A azurin (45).…”

Biomimetic Applications of Metal Systems Supported by Scorpionates

“…Model complexes have been reported to reproduce the peculiar structure and spectroscopic features of blue copper proteins Kitajima et al, 1992;Holland & Tolman, 1999;, or the function of these biological electron carriers (Rorabacher, 2004). The major synthetic challenges to yield structural/spectroscopic models have been: 1) obtain Cu(II)-thiolate species, without the concomitant formation of disulfides and Cu(I) (Mandal et al, 1997), and 2) provide complexes exhibiting distorted tetrahedral coordination of Cu(II), which mostly prefers a tetragonal environment. Substituted tris(pyrazolyl)borate ligands were originally employed in order to fulfil these requirements (Kitajima & Tolman, 1995), since they are tetrahedral enforcers and furnish enough electron density to copper to disfavor oxidation of thiolate coligands (Bruce & Ostazewski, 1973;Churchill et al, 1975).…”

Coordination Aspects in Modern Inorganic Chemistry

“…Among them, we note copper-chalcogene chelates [63,64,66,67], modeling active centers of blue copper proteins 101-103. In early studies [63,64], there were cross-linked (Z) copper complexes of bis-thiosalicylidenethylenediamine and its analogues of the type 101. Later on ( [67] and refs.…”