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The palladium-catalyzed sp-sp2 C−C bond forming the Sonogashira reaction has been both extensively studied mechanistically and widely used in organic synthesis. Herein, we describe an investigation into how a palladium(II) complex with arylazoformamide (AAF) ligands mediates these transformations. When mixed, two AAFs coordinate in a κ1-fashion with an equivalent of PdCl2, creating complexes of the form PdCl2(AAF)2. Under typical and optimized copper(I)-cocatalyzed Sonogashira conditions, using phenylacetylene and iodobenzene as reagents, these complexes (precatalysts) reduce to Pd(0) and afford the coupled diphenylacetylene product in high yields (i.e., 99%). A substrate scope explored the substitution on both rings, yielding 18 examples with yields varying from 38 to 99%. Mechanistically, from DFT studies, a formal Pd(I) open-shell singlet complex is suggested, along with an explanation of the need for DBU when employing CuI in toluene. Further DFT exploration provides insight into the copper-free Sonogashira reaction when utilizing Pd(AAF)2 complexes. 

The design of a rigidified macrocyclic N-heterocyclic carbene (NHC) ligand led to the formation and structural characterization of in- and out-Ru carbene complexes. In this study, introduction of a conformational lock was used to rigidify heteroaryl-aryl bonds and thereby enforce a more perpendicular dihedral angle. A forcing metalation step was needed to form the isomeric Ru carbene complexes (Grubbs complexes). The major isomer had the Ru carbene fragment located outside the macrocyclic ring whereas the minor isomer had the Ru carbene inside the macrocyclic ring. The two new Ru carbene complexes are the first examples of in- and out-isomers of a Grubbs-type complex. The solid state structures of each isomeric ruthenium carbene complex was determined by x-ray diffraction studies. The two Ru complexes showed significantly different catalytic reactivity in the ring-closing metathesis (RCM) of the benchmark substrate, diethyl diallylmalonate. We performed computational studies to determine rotational barriers; scalable energetic barriers were found in the unmetallated NHC ligand, favoring the in-isomer by 2.4 kcal/mol. These calculations, coupled with attempted interconversion of isomers, support a mechanism featuring rotational isomerization of the NHC nucleophile in a preequilibrium step before metalation. 

A group of iron complexes supported by a 2,6-diisopropylphenyl-substituted β-dialdiminate ligand have been prepared and characterized. The iron(II) chloride complex forms as the lithium chloride adduct that can be compared directly to its methyl-substituted β-diketiminate analog, revealing a more open iron center in the β-dialdiminate complex with a remarkable degree of rotation about the 2,6-diisopropylphenyl substituent. Exchange of chloride with phenylacetylide ligands generates a related four-coordinate organometallic complex. Interestingly, the iron(I) phenylacetylene complex is unstable in solution, undergoing bimetallic coupling to generate an isomeric mixture of bimetallacyclic complexes. We propose that this process stems from increased flexibility in the β-dialdiminate ligand backbone and highlights the exciting opportunities that are presented by this system.