Influence of Fine Ligand Substitution Modification of the Isocyanidometal Bridge on Metal-to-Metal Charge Transfer Properties in Class II-III Mixed Valence Complexes.

The synthesis and characterization of Class II-III mixed valence complexes have been an interesting topic due to their special intermediate behaviour between localized and delocalized mixed valence complexes. To investigate the influence of the isocyanidometal bridge on metal-to-metal charge transfer (MMCT) properties, a family of new isocyanidometal-bridged complexes and their one-electron oxidation products cis-[Cp(dppe)Fe-CN-Ru(L)2 -NC-Fe(dppe)Cp][PF6 ]n (n=2, 3) (Cp=1,3-cyclopentadiene, dppe=1,2-bis(diphenylphosphino)ethane, L=2,2'-bipyridine (bpy, 1[PF6 ]n ), 5,5'-dimethyl-2,2'-bipyridyl (5,5'-dmbpy, 2[PF6 ]n ) and 4,4'-dimethyl-2,2'-bipyridyl (4,4'-dmbpy, 3[PF6 ]n )) have been synthesized and fully characterized. The experimental results suggest that all the one-electron oxidation products may belong to Class II-III mixed valence complexes, supported by TDDFT calculations. With the change of the substituents of the bipyridyl ligand on the Ru centre from H, 5,5'-dimethyl to 4,4'-dimethyl, the energy of MMCT for the one-electron oxidation complexes changes in the order: 13+ <23+ <33+ , and that for the two-electron oxidation complexes decreases in the order 14+ >34+ >24+ . The potential splitting (ΔE1/2 (2)) between the two terminal Fe centres for N[PF6 ]2 are the largest potential splitting for the cyanido-bridged complexes reported so far. This work shows that the smaller potential difference between the bridging and the terminal metal centres would result in the more delocalized mixed valence complex.