The electronic structures of the highly air-sensitive intermediates (N⁁N)(C5Me5)Rh, (N⁁N = 2,2′-bipyridine (bpy), 2,2′-bipyrimidine (bpym), 2,2′-bipyrazine (bpz) and 3,3′-bipyridazine (bpdz)) of hydride transfer catalysis schemes were studied through resonance Raman (rR) spectroscopy and through EPR of the reduced forms [(N⁁N)(C5Me5)Rh]˙−. The rR results are compatible with a predominant MLCT character of the lowest excited states [(N⁁N)(C5Me5)Rh]*, and the EPR spectra of the reduced states reveal the presence of anion radical ligands, (N⁁N)˙−, coordinated by unusually electron rich rhodium(I) centres. The experimental results, including the assignments of electronic transitions, are supported by DFT calculations for the model compounds [(N⁁N)(C5H5)Rh]o/˙−, N⁁N = bpy or bpym. The calculations confirm a significant but not complete mixing of metal and ligand orbitals in the lowest unoccupied MO which still retains about ¾
π*(N⁁N) character. DFT calculations on (bpy)(C5H5)M and [(bpy)(C5H5)ClM]+, M = Co, Rh, Ir, agree with the experimental results such as the differences between the homologues, especially the different LUMO characters of the precursor cations in the case of Co (→dM) and Rh or Ir (→π*(bpy)).