London dispersion constitutes one of the fundamental interaction forces between atoms and between molecules. While modern computational methods have been developed to describe the strength of dispersive interactions in the gas phase properly, the importance of inter- and intramolecular dispersion in solution remains yet to be fully understood because experimental data are still sparse in that regard. We herein report a detailed experimental and computational study of the contribution of London dispersion to the bond dissociation of proton-bound dimers, both in the gas phase and in dichloromethane solution, showing that attenuation of inter- and intramolecular dispersive interaction by solvent is large (about 70% in dichloromethane), but not complete, and that current state-of-the-art implicit solvent models employed in quantum-mechanical computational studies treat London dispersion poorly, at least for this model system.

Essential to biological activity of adenosylcobalamin (AdoCbl) and methylcobalamin (MeCbl) is the Co-C bond cleavage step. Hence, we report an accurate determination of the homolytic gas-phase Co-C bond dissociation energies in the related adenosyl- and methylcobinamides (41.5 ± 1.2 and 44.6 ± 0.8 kcal/mol, respectively) utilizing an energy-resolved threshold collision-induced dissociation technique. This approach allows for benchmarking of electronic structure methods separate from (often ill-defined) solvent effects. Adequacy of various density functional theory methods has been tested with respect to the experimentally obtained values.

The biological properties of trifluoromethyl compounds have led to their ubiquity in pharmaceuticals, yet their chemical properties have made their preparation a substantial challenge, necessitating innovative chemical solutions. We report the serendipitous discovery of a borane-catalyzed formal C(sp3)-CF3 reductive elimination from Au(III) that accesses these compounds by a distinct mechanism proceeding via fluoride abstraction, migratory insertion, and C-F reductive elimination to achieve a net C-C bond construction. The parent bis(trifluoromethyl)Au(III) complexes tolerate a surprising breadth of synthetic protocols, enabling the synthesis of complex organic derivatives without cleavage of the Au-C bond. This feature, combined with the “fluoride-rebound” mechanism, was translated into a protocol for the synthesis of 18F-radiolabeled aliphatic CF3-containing compounds, enabling the preparation of potential tracers for use in positron emission tomography.

Carbene polymerization provides polyolefins that cannot be readily prepared from olefin monomers; however, controlled and living carbene polymerization has been a long-standing challenge. Here we report a new class of initiators, (π-allyl)palladium carboxylate dimers, which polymerize ethyl diazoacetate, a carbene precursor in a controlled and quasi-living manner, with nearly quantitative yields, degrees of polymerization >100, molecular weight dispersities 1.2-1.4, and well-defined, diversifiable chain ends. This method also provides block copolycarbenes that undergo microphase segregation. Experimental and theoretical mechanistic analysis supports a new dinuclear mechanism for this process.

Migratory insertion of carbon-based species into transition-metal–carbon bonds is a mechanistic manifold of vast significance: it underlies the Fischer–Tropsch process, Mizoroki–Heck reaction, Ziegler–Natta and analogous late-transition-metal-catalyzed olefin polymerizations, and a number of carbonylative methods for the synthesis of ketones and esters, among others. Although this type of reactivity is well-precedented for most transition metals, gold constitutes a notable exception, with virtually no well-characterized examples known to date. Yet, the complementary reactivity of gold to numerous other transition metals would offer new synthetic opportunities for migratory insertion of carbon-based species into gold–carbon bonds. Here we report the discovery of well-defined Au(III) complexes that participate in rapid migratory insertion of carbenes derived from silyl- or carbonyl-stabilized diazoalkanes into Au–C bonds at temperatures ≥ −40 °C. Through a combined theoretical and experimental approach, key kinetic, thermodynamic, and structural details of this reaction manifold were elucidated. This study paves the way for homogeneous gold-catalyzed processes incorporating carbene migratory insertion steps.