Dinuclear compounds electrochemistry

The electrochemistry of the dinuclear compound has also been investigated this compound undergoes a one-electron oxidation (+0.35 V vs. SCE) in pyridine to yield a species which is presumably mixed valent. It also undergoes a four-electron reduction (at —0.9 V) to yield two... 

Iron-sulfur cluster compounds, 1203 dinuclear, 235 electrochemistry, 236 hexanuclear, 241 mononuclear, 235 tetranuclear, 238 trinuclear, 237 Isomerization iridium catalysts, 1158... 

Reaction of the neutral complex [CpFe(ri5-CgHg-l-exo-Nu)] (Nu = CH(CC>2Et)2, H) with [CpCo(Ti2-C2H4)2] afforded32i the thermally labile diamagnetic heterodinuclear, cyc/o-Cg bridged FeCo complexes [ (CpFe)(CpCo) p-(Ti7-CgHg-l-exo-Nu)]. The chemistry and electrochemistry of the dinuclear compounds and their decomposition products were described. 

Very interesting and detailed oxidation patterns have been obtained for the dinuclear species [(bpy)2Ru(2,3-dpp)Ru(bpy)2]4+ (Ru2) and [(bpy)2Ru(2,5-dpp) Ru(bpy)2]4+ (Ru2a)21,22 (see Fig. 5.3 and Table 5.1), which contain a relatively small number of redox centers and can be considered as the most effective model compounds to understand the electrochemistry of the complexes of higher nuclearity. In the dinuclear species, the knowledge of the voltammetric behavior of the mononuclear building blocks allowed to establish the localization for each redox process and to evaluate the mutual interactions existing between the redox sites. 

The synthesis of several niobium porphyrins has been described in the literature, but the electrochemistry of these compounds is limited to mononuclear derivatives of (P)Nb 0(02CMe) and (P)NbO,whereP = OEPorTPP [138-140] and dinuclear derivatives of [(P)Nb]203 where P = T(p-CH3)PP or OEP [141]. 

Harutyunyan et al. investigated the formation of the chiral Cu(I)-diphosphine complexes, as part of a comprehensive mechanistic study on the Cu(I)-catalysed ACA of Grignard reagents to a,p-unsaturated carbonyl compounds [127]. Based on NMR, ESI-MS, IR, electrochemistry and X-ray ciystaUography measurements, they concluded that halide-bridged dinuclear copper complexes Cl (Scheme 30) are formed and persist in the solvents typically used for the ACA (Et20, tBuOMe and CH2CI2). 

---