Methide Affinity Scale: Key Thermodynamic Data Underpinning Catalysis, Organic Synthesis, and Organometallic and Polymer Chemistry.

Methide transfer reactions play important roles in many areas of chemistry, including the Grignard reaction, in the transmetalation steps of metal-catalyzed cross-coupling reactions, and in the generation of cationic metal polymerization catalysts. Methide affinities (MAs) are the key thermodynamic quantity that underpin such reactions, and yet comprehensive methide affinity scales are poorly developed. Here, B3LYP-D3BJ/def2-TZVP calculations are used to calculate the energy changes (MAs) for cations (MeZ → Z + Me), neutrals (MeY → Y + Me), and anions (MeX → X + Me) derived from permethyl species of all group s and p elements.

Ion-pairs as a gateway to transmetalation: aryl transfer from boron to nickel and magnesium.

Gas-phase ion-ion reactions between tris-1,10-phenantholine metal dications, [(phen)M] (where M = Ni and Mg), and the tetraphenylborate anion yield the ion-pairs {[(phen)M][BPh]}. The ion-pairs undergo transmetalation upon loss of a phen ligand to give the organometallic complexes [(phen)M(Ph)]. DFT calculations, used to determine the energy barriers for the transmetalation reactions and the hydrolysis reactions, are entirely consistent with the experimental results.

Identification of the Side Products That Diminish the Yields of the Monoamidated Product in Metal-Catalyzed C-H Amidation of 2-Phenylpyridine with Arylisocyanates.

The Ru(II)-catalyzed amidation of 2-arylpyridines with aryl isocyanates via C-H bond activation is less efficient than described previously, due to the formation of a series of side products, which were readily identified using direct infusion electrospray mass spectrometry and high-performance liquid chromatography-mass spectrometry.