Polyyn-diyls capped by Ru(2)(ap)(4) termini (ap = 2-anilinopyridinate), that is, [Ru2(ap)4](mu-C,C'-C2m)[Ru2(ap)4] (compounds 1-5 with m = 1-4 and 6), were synthesized through either a metathesis reaction between Ru2(ap)4Cl and LiC(2m)Li or a Glaser homocoupling reaction of Ru2(ap)4(CmH) under Eglinton/Hay conditions. X-ray diffraction studies of compounds 2 and 4 revealed both the linear rigid rod topology of these compounds and the fine structural details about the Ru2 cores and polyyn-diyl chains. Cyclic and differential pulse voltammetric (CV and DPV) measurements and spectroelectrochemical studies show that reduced and oxidized forms of 1, 2, 4, and 5 are donor-acceptor systems in which the Ru2 termini are coupled to varying degrees depending upon the length of the polyyn-diyl bridge.
A highly efficient palladium-catalyzed acylative cross-coupling of carboxylic amides with arylboronic acids has been achieved via synergistic activation of the C(acyl)-N bond by independently modifiable activating groups. Coupling of amides features not only good functional group tolerance but also modifiable reactivities to overcome steric hindrance.
Rich electrochemistry and strong electronic couplings across the carbon bridges are revealed for compounds composed of two tetra(m-N,NA-2-anilinopyridinate)diruthenium(II,III) termini bridged by either butadiynediyl (1) or ethynediyl (2) ligands.
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