Combined Kinetic and Computational Analysis of the Palladium-Catalyzed Formylation of Aryl Bromides.

Aryl aldehydes are key synthetic intermediates in the manufacturing of active pharmaceutical ingredients. They are generated on scale (>1000 kg) through the palladium-catalyzed formylation of aryl bromides using syngas (CO/H). The best-in-class catalyst system for this reaction employs di-1-adamantyl--butylphosphine (cataium A), palladium(II) acetate, and tetramethylethylenediamine.

A Continuous Flow Process for the Defluorosilylation of HFC-23 and HFO-1234yf.

A continuous flow process has been developed for the defluorosilylation of trifluoromethane (HFC-23) and 2,3,3,3-tetrafluoropropene (HFO-1234yf) through reaction with lithium silanide reagents under inert conditions. Design of experiment optimization improved process conditions, including productivity, yields, reduction of solvent use, and gas destruction. The small chain fluorinated organosilane products RSiCFH and RSiCHC(F)═CF were competent nucleophiles in the fluoride-catalyzed difluoromethylation of aldehydes, and trifluoroallylation of aldehydes, ketones, and imines.

A Paramagnetic Nickel-Zinc Hydride Complex.

Reaction of a molecular zinc-hydride [{(ArNCMe)CH}ZnH] (Ar=2,6-di-isopropylphenyl) with 0.5 equiv. of [Ni(CO)Cp] led to the isolation of a nickel-zinc hydride complex containing a bridging 3-centre,2-electron Ni-H-Zn interaction.

Dyotropic Rearrangement of an Iron-Aluminium Complex.

Ligand exchange processes at metal complexes underpin their reactivity and catalytic applications. While mechanisms of ligand exchange at single site complexes are well established, occurring through textbook associative, dissociative and interchange mechanisms, those involving heterometallic complexes are less well developed. Here we report the reactions of a well-defined Fe-Al dihydride complex with exogenous ligands (CO and CNR, R=Me, Bu, Xyl=2,6-MeCH).