Solid-state Sc NMR studies of Cp*Sc-X and Cp*ScX(THF).

Cp*Sc-X, where X is a halide, were synthesized and studied by solid-state Sc NMR to determine how the Sc-X bond affects quadrupolar NMR parameters. The experimental quadrupolar coupling constants (C) show that the fluoride has the largest coupling constant and that the iodide has the smallest coupling constant. DFT analysis of this data indicates that the C of these compounds is related to core scandium and halide orbitals, which is related to polarizability of the halide and the Sc-X distance.

The β-Agostic Structure in (C Me ) Sc(CH CH ): Solid-State NMR Studies of (C Me ) Sc-R (R=Me, Ph, Et).

Multinuclear solid-state NMR studies of Cp* Sc-R (Cp*=pentamethylcyclopentadienyl; R=Me, Ph, Et) and DFT calculations show that the Sc-Et complex contains a β-CH agostic interaction. The static central transition Sc NMR spectra show that the quadrupolar coupling constants (C ) follow the trend of Ph≈Me>Et, indicating that the Sc-R bond is different in Cp* Sc-Et compared to the methyl and phenyl complexes. Analysis of the chemical shift tensor (CST) shows that the deshielding experienced by Cβ in Sc-CH CH is related to coupling between the filled σ orbital and the vacant πSc⋯HC* orbital.

High-Yield Production of Fatty Nitriles by One-Step Vapor-Phase Thermocatalysis of Triglycerides.

Fatty nitriles are widely used as intermediate molecules in the pharmaceutical and polymer industries. In addition, hydrogenation of fatty nitriles produces fatty amines that are common surfactants. In the conventional fatty nitrile process, triglycerides are first hydrolyzed and the resulting fatty acids are catalytically reacted with NH in a liquid-phase reaction.

Selective hydrosilylation of alkynes and ketones: contrasting reactivity between cationic 3-iminophosphine palladium and nickel complexes.

The catalytic hydrosilylation of alkynes and ketones has been explored utilizing palladium- and nickel(allyl) complexes supported by 3-iminophosphine ligands. Palladium and nickel demonstrated distinctly different reactivity profiles, with palladium proving very effective for the hydrosilylation of electron-deficient alkynes, while nickel excelled with ketones and internal alkynes. Additionally, in many cases, regioselective hydrosilylation was observed.

Cationic [(Iminophosphine)Nickel(Allyl)] Complexes as the First Example of Nickel Catalysts for Direct Hydroamination of Allenes.

The first example of nickel-catalyzed hydroamination of allenes is reported. The new cationic [(3-iminophosphine)nickel(allyl)] catalysts have been fully characterized and act regioselectively in the catalytic hydroamination of allenes with secondary amines at room temperature.

Highly efficient regioselective hydrosilylation of allenes using a [(3IP)Pd(allyl)]OTf catalyst; first example of allene hydrosilylation with phenyl- and diphenylsilane.

A [(3IP)Pd(allyl)]OTf complex was shown to function efficiently and regioselectively in allene hydrosilylation with phenyl- and diphenylsilane. The catalyst also proved to be highly active for allene hydrosilylation employing a wide range of silanes, each of which produced a single regioisomer.