The Divergent Reduction Chemistry of Ln(II) Bis(terphenylthiolate) Complexes, Ln(SAr^<i>i</i>Pr6)₂, Leads to KLn(μ-SAr^<i>i</i>Pr6)₂, C─H Bond Activation Products, and Two-Electron Reduction Reactivity

Potassium graphite (KC₈) reduction of the terphenylthiolate La(II) and Nd(II) complexes, Ln(SAr^<i>i</i>Pr6)₂, <b>1-Ln</b> (SAr^<i>i</i>Pr6 = C₆H₃-2,6-(C₆H₂-2,4,6-^<i>i</i>Pr₃)₂; Ln = La, Nd), forms KLn(μ-SAr^<i>i</i>Pr6)₂, <b>2-Ln</b>, which displays characteristic metal-arene interactions involving the flanking ring of the sterically bulky ligand. In contrast, when the Yb(II) complex, Yb(SAr^<i>i</i>Pr6)₂, is treated with KC₈, C-H bond activation of a ligand yielded an Yb(II) complex of a dianionic ligand, Yb{SC₆H₃-2-(C₆H₂-2,4,6-^<i>i</i>Pr₃)-6-[C₆H₂-2,6-^<i>i</i>Pr₂-4-C(CH₃)₂]}(OEt₂)₂, <b>3</b>. <b>2-La</b> functions as a two-electron reductant in its reaction with iodomethane to form the terminal methyl complex La(SAr^<i>i</i>Pr6)₂(CH₃), which provides a new synthetic route to Ln-C bonds using electrophilic reagents.