Electron Paramagnetic Resonance and Spectroscopic Characteristics of Electrogenerated Mixed-Valent Systems (h5-C5Me5)M(m-L)M(h5-C5Me5)+ (M = Rh, Ir; L = 2,5-Diiminopyrazines) in Relation to the Radicals (h5-C5Me5)ClM(m-L)MCl(h5-C5Me5)+ and (h5-C5Me5)M(m-L)MCl(h5-C5Me5)2+
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Inorganic Chemistry 39 (12): 2516--2521 (2000)

Electrochem. redn. of the dinuclear (h5-C5Me5)ClM(m-L)MCl(h5-C5Me5)2+ ions (M = Rh, Ir; L = 2,5-bis(1-phenyliminoethyl)pyrazine (bpip) and 2,5-bis1-(2,6-dimethylphenyl)iminoethylpyrazine (bxip)) proceeds via the paramagnetic intermediates (h5-C5Me5)ClM(m-L)MCl(h5-C5Me5)+ (L = bpip) or (h5-C5Me5)M(m-L)MCl(h5-C5Me5)2+ (L = bxip) and (h5-C5Me5)M(m-L)M(h5-C5Me5)+. Whereas the first is clearly a radical species with a small g anisotropy, the chloride-free cations are distinguished by structured intervalence charge transfer (IVCT) bands in the near-IR region and by rhombic ESR features between g = 1.9 and g = 2.3, which suggests considerable metal participation at the singly occupied MO. Alternatives for the d configuration assignment and for the role of the bisbidentate-conjugated bridging ligands will be discussed. The main difference between bpip and bxip systems is the destabilization of the chloride-contg. forms through the bxip ligand for reasons of steric interference. on SciFinder(R)
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