Redox directing ligands on metal complexes offer a pathway to developing materials for photochemistry. With the rhodium complexes under examination, there is particular interest in their electrochemistry related to the splitting of water. For the purposes of the reduction half reaction of two protons to hydrogen, the new rhodium(I) complex, Rh(phi)(nacnacF6) (phi = 9,10-phenanthrenediimine; nacnacF6 = CH[C(CF3)(N-iPr2C6H3)]), was prepared in 88% yield by the reaction of the phi ligand with Rh(nacnacF6)(CO)2. The new complex was characterized by 1H, 13C and 19F NMR, IR, and UV-Vis spectroscopies. Cyclic voltammetry was used to observe redox properties of the complex, revealing one-electron oxidative and reductive processes at 0.37 and -1.70 V vs Cp2Fe+/Cp2Fe. The rhodium(I) complex also undergoes oxidative addition reactions with halogen reagents, in the case of Br2 forming the trans- oxidative addition product, RhI(phi)(nacnacF6)Br2, which was characterized spectroscopically and by single crystal X-ray diffraction experiments.

Synthesis of rhodium complexes toward a proton reduction electrocatalyst

239th National Meeting (2010)

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