Spectroscopic and electrochemical properties of the isomeric bidiazine complexes (C5Me5)ClRh(bdz)+ and (C5Me5)Rh(bdz) and their relevance to the catalysis of the 2 H+ $\rightarrow$ H2 reaction by 2,2'-bipyridine analogs
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Journal of Organometallic Chemistry 419 (1-2): 233--243 (1991)

Electronic structures and ligand effects were studied for the isomeric Rh(III/I) complexes (C5Me5)ClRh(bdz)(X) (X- = Cl-, PF6-; bdz = 3,3'-bipyridazine, 2,2'-bipyrazine, 2,2'- and 4,4'-bipyrimidine) and (C5Me5)Rh(bdz). Comparative NMR and UV-visible spectroscopic and cyclic-voltammetry measurements in aprotic solvents allowed definition of a frontier-MO situation that was correlated with the reactivity of the (C5Me5)ClRh(bpy)+ system as a catalyst for H evolution from H2O. Thus, while the potential for the 2-electron redn. of the Rh(III) halide precursor depends on the ligand basicity, the MO description shows that there is extremely strong p-back donation and orbital mixing between the d orbitals of the H+-accepting (C5Me5)Rh(I) fragment and the acceptor level of the heterocyclic ligand. on SciFinder(R)
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