Macrocycles dithiocarbamate

Interesting results were reported with dithiocarbamates derived from diamines. Thus, a series of dinuclear zinc(II), cobalt(II), and nickel(II) dithiocarbamate ditopic macrocyclic receptors containing various spacer groups of different sizes has been reported.412,413,414 Spectroscopic investigations and... 

Coordinated transition metal redox-active macrocycles, 39 108-124 ammonium cation, 39 128-133 crown ether and bis crown ether ligands containing bipyridyl transition metal recognition sites, 39 111 crown ether dithiocarbamate and dithiolene complexes, 39 123-124 metalloporphyrin crown ether compounds, 39 108-109... 

There have been two books that contain compilations of the electrochemistry of Os (572,573). There have also been reviews that cover the electrochemistry of certain classes of complexes with ligands such as porphyrins (142), dithiocarbamates (463), and macrocyclic complexes (39, 93). The purpose of this section is not to provide a comprehensive review of electrochemical studies over recent years, but rather to give some insight into the factors that affect the redox potentials and their use in obtaining information about 7r bonding and backbonding. Particular emphasis is placed on the similarities and differences between analogous Os and Ru complexes. 

In a serendipitous fashion, a novel mixed valence tetranuclear copper(II)/copper(III) dithiocarbamate [2]catenane was prepared in near quantitative yield by partial chemical oxidation of a preformed dinuclear copper(II) naphthyl dtc macrocycle (Scheme 6).49 X-ray structure, magnetic susceptibility, ESMS and electrochemical studies all support the tetranuclear catenane dication formulation. The combination of the lability of copper(II) dtc coordinate bonds and favourable copper(II) dtc-copper(III) dtc charge transfer stabilisation effects are responsible for the high yielding formation of the interlocked... 

Oxidation of Co111 dithiocarbamates gives [Co(dtc)3]+ complexes which are low-spin d5 with magnetic moments between 2.2 and 2.7 BM. For the macrocyclic complex (17-F-IX) (formally CoIV) square geometry was confirmed by X-ray diffraction the compound has one unpaired electron and slowly oxidizes water, with reduction to H[Com(L)].M... 

Many dithiocarbamate complexes of zinc, silver, cadmium or mercury improve emulsion stability, including bis(dibenzyldithiocarbamato)-zinc(II) or -cadmium(II) and silver(I) diethyldi-thiocarbamate. Cadmium salts, mixed with citric acid or tartaric acid and added to the emulsion, are reported to be effective. Mercury(II) complexes of ethylenediaminetetraacetic acid (EDTA) and related ligands and of solubilized thiols such as (4) can be used. Other coordination compounds reported include EDTA and related ligand complexes of Co and Mn, mixtures of Co salts with penicillamine (5) and macrocyclic complexes of Ag such as (6). The latter compounds may be used in diffusion transfer systems in which transferred maximum densities are stabilized. 

Dithiocarbamate ligands have some structural similarities with carboxylates and their coordination chemistry has been explored extensively. Interestingly, their application in metallosupramolecular chemistry is almost unexplored so far, and there are only three reports on structurally characterized macrocycles derived from bis(dithiocarbamates) (Figure 2.5.12)." ... 

Figure 2.5.12 Organotin macrocycles derived from bis(dithiocarbamates) as organic connectors...

Treatment of Z>fr(butylaminomethyl)biphenyl, other spacers were also used, with CS2 and base generated the Z>fr(dithiocarbamate) ligand (dtc), which with Cu(OAc)2 generated the binuclear copper(ll) dtc macrocycle, then subsequent reaction with NaAuCU gave the novel heteropolymetallic Cu(ll)-Au(lll) catenane <05CC2214>. 

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