Gold complexes mixed-valence compounds

L = py or H2O) undergo solvolysis and oxidation to yield the mixed-valence compound [(bpy)2(0)Ru(V)0Ru(III)(py)(bpy)2r , which is an effective electrocatalyst for the oxidation of d to CI2 at pH < 4 and Cl" to OCr at pH > 11.8. Chloride ions have also been implicated as mediators in the oxidation of tetracyano-platinate(II) by gold(III) complexes and in the reversible redox reaction between trans,cis-[PtCl2(L)2(am)2] and [Pt(diars)2]. In both cases an atom-transfer redox mechanism is suggested. 

Ylide complexes of gold are unique in that they exhibit an exceptional chemical and thermal stability, which facilitates preparative and structural work very considerably. It was in this class of compounds that a large variety of true organogold(ll) and mixed valence organogold(l)/(lIl) complexes was discovered. These are rare in the remainder of organogold chemistry. 

Electric fleld gradient, 22 214-218 Electroabsorption spectroscopy, 41 279 class II mixed-valence complexes, 41 289, 291, 294-297 [j(jl-pyz)]=+, 41 294, 296 Electrocatalytic reduction, nickel(n) macro-cyclic complexes, 44 119-121 Electrochemical interconversions, heteronuclear gold cluster compounds, 39 338-339 Electrochemical oxidation, of iron triazenide complexes, 30 21 Electrochemical properties fullerene adducts, 44 19-21, 33-34 nickeljll) macrocyclic complexes, 44 112-113... 

Fe2(III,III)2+ states. By considering that organometallic dendrimers based on conjugated ferrocene units are of special importance since mixed-valence states have interesting electrical, redox, and magnetic properties, recently three generations of polypropylene amine) dendrimers, decorated at their periphery with 4, 8, and 16 (compound 6, Fig. 6.6a) BFc units, respectively, have been synthesized and the electrochemical behavior of the dendrimers complexed with (3-cyclodextrins ([3-CD) and adsorbed at self-assembled monolayers (SAMs) of heptathioether-functionalized [3-CD on gold (molecular printboard) has been studied.40... 

Another example of an eight-membered metallocycle containing Au(II) centers is the dithiocarbamate complex (9) (20), obtained from the gold(I) dithiocarbamate complex (8) with halogens or pseudohalogens at -78° in C. However, these compounds disproportionate to form mixed-valence salts (10). It was shown that the vCs band of the coordinated dithiocarbamate is sensitive to the oxidation state of the gold, increasing in the order 1495, 1523, and 1547 cm-1 for the Au(I), Au(II), and Au(III) complexes, respectively (20). 

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