ABSTRACT
The electrosynthesis of Rh(2)(dpf)(4)(R) where dpf is the N,N'-diphenylformamidinate anion and R = CH(3), C(2)H(5), C(3)H(7), C(4)H(9) or C(5)H(11) was carried out in THF containing 0.2 M tetra-n-butylammonium perchlorate (TBAP) and one of several alkyl iodides represented as RI. The initial step in the reaction involved a one-electron reduction of the Rh(2)(4+) unit in Rh(2)(dpf)(4) to its Rh(2)(3+) form followed by a homogeneous reaction involving electrogenerated [Rh(2)(dpf)(4)](-) and the alkyl iodide in solution to give Rh(2)(dpf)(4)(R). The homogeneously generated Rh(2)(5+) product was then immediately reduced by a second electron at the potential where [Rh(2)(dpf)(4)(R)](-) is generated, giving [Rh(2)(dpf)(4)(R)](-) which contains a Rh(2)(4+) center as a final product of an electrochemical ECE mechanism. The electrosynthesized [Rh(2)(dpf)(4)(CH(3))](-) derivative could be reoxidized to Rh(2)(dpf)(4)(CH(3)) on the reverse potential sweep and both forms of the CH(3) bonded derivative were in situ characterized by cyclic voltammetry combined with UV-visible and/or ESR spectroscopy. The reversible Rh(2)(4+/3+) process of Rh(2)(dpf)(4) is located at E(1/2) = -1.11 V in THF, 0.2 M TBAP while the electrogenerated Rh(2)(dpf)(4)(R) products are substantially easier to reduce, with E(p) values for the Rh(2)(5+/4+) couples ranging from -0.50 to -0.54 V vs. SCE depending upon the specific R group.