Trinuclear Ruthenium Cluster Dimers

Trinuclear ruthenium cluster dimers of the type [Ru30(CH3C00)6(C0)(L)]2 (p-BL), where L = 4-dimethylaminopyridine (dmap) 1, pyridine (py) 2, or 4-cyanopyridine (cpy) 3 BL = pyrazine (Figure 5.3), first synthesised by Ito... 

Although the cyclic voltammetry for this complex seems fairly similar to the trinuclear ruthenium cluster dimers, the lower-lying LUMO (as evidenced by the lower reduction potential) of the triazine bridging ligand plays an important role in explaining the details of the spectroelectrochemistry observed for this LCD. The CO stretching frequency of the neutral complex appears at 1940 cm Upon application of— 1.050 V (vi. Ag pseudoreference, roughly 0 to... 

Analysis of the spectral lineshapes of 5 and 6 gave an uphill rate for charge transfer of 6.5 x lO" s (Table 5.2), and an equilibrium constant of 2.2 for the charge distribution, which compares well with previously reported rate constants for similar mixed-valence dimers of trinuclear ruthenium clusters. 

These iron and ruthenium dimers are exceedingly robust compounds. Indeed decomposition of trinuclear phosphidoacetylide-bridged clusters invariably yields these molecules as major decomposition products ... 

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