Cobalt diimine complexes, reaction with

Similar results were obtained for the redox reactions of a series of cobalt diimine complexes with cytochrome c (156, 157). In general a good agreement exists between the kinetically and thermodynami-... 

A number of dinuclear cobalt dioxygen complexes with polyamine type ligands (pyen, pydien, amp) have been reported to undergo oxidative dehydrogenation in water at 35 [5,17,23,24]. These reactions are base catalyzed and lead to the formation of mono- and diimines in which the C=N bonds are conjugated with an aromatic ring. In addition to UV and IR evidence, the monoimine intermediate has been detected via hydrolysis to the aldehyde. The proposed reaction paths are shown for the pydien system in Scheme 1. 

When a metal ion such as nickel (II) is absent, thiazoles and mercaptals are formed. Such reactions have been carried out in which the diketone was biacetyl, 2,3-pentanedione, 2,3-octanedione, l-phenyl-l,2-propane-dione, and 1,2-cyclohexanedione (51). In like manner, the tris complexes of W,W -dimethyl-2,3-butane diimine with iron(II), cobalt(II), and nickel(II) may be prepared from methylamine and biacetyl when the appropriate metal ion (27j 28j 41) is present. Replacing methylamine with hydroxylamine causes the formation of a-dioximes (13). 

The condensation of 2V,A -bis(3-aminopropyl)ethylenediamine (7V,A -ethylene-bis[l,3-propanediamine]) as its acid salt with 2,3-butanedione (biacetyl) in the presence of cobalt(II) or nickel(II) acetate gives complexes of 2,S-Mej [14] - 1,3-diene-l,4,8,11-N4 containing one a-diimine linkage. Experiments have shown that the presence of H ion determines whether or not a macrocyclic complex forms and that, in the presence of H, the time at which the metal acetate is added to the reaction mixture influences the yield of the complex. Unlike the reaction between biacetyl and 1,3-propanediamine to form 2,3,9,10-Me4[14]-1,3,8,10-tetraene-l,4,8,11-N4 (Sec. 4), the condensation of biacetyl withTVA -bis(3-aminopropyl)ethylenediamine is particularly sensitive to excess acetate so that the procedures given use the optimized conditions. 

Recent studies have shown that coordinated ammonia and amine ligands under basic conditions may effect nucleophilic attack at carbonyl centres in organic compounds, " These reactions occur due to formation of deprotonated amido species which can act as nucleophiles. For example, reaction of cobalt(III) and platinum(IV)ammines with ketones gives the corresponding Co and Pt imine complexes. A similar reaction between [Ru(NH3)6] and diones produces the corresponding Ru diimine (108). It has also been found that nitrilepentaammineruthenium(II)... 

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