Abstract
Cross-coupling reactions between terminal ethynes (HC⋮CY) and Ru2(ap)4(C2(k-1)H) under Hay conditions, where ap is 2-anilinopyridinate and k = 2−5, resulted in compounds Ru2(ap)4(C2kY) (Y = SiiPr3 and Ph) along with the homocoupling products YC4Y and [Ru2(ap)4]2(μ-C4(k-1)). Compounds Ru2(ap)4(C2kY) display two reversible Ru2-based one-electron couples: an oxidation and a reduction. The HOMO−LUMO gaps (Eg) estimated from electrode potentials correlate linearly with the number of acetylenic bonds (k) within each series. Both nonlinear absorption and degenerate four-wave mixing measurements were carried out at both 532 and 800 nm with nano- and femtosecond laser pulses.
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