A periodic mesoporous organosilica material functionalized with a Pd N‐heterocyclic carbene complex was synthesized by applying an electrostatic grafting method. The resulting hybrid material was characterized by solid‐state 29Si and 13C cross‐polarization magic‐angle spinning NMR spectroscopy, XRD, thermogravimetric analysis, and BET measurements. The hybrid was applied as a catalyst for the Suzuki–Miyaura cross‐coupling between aryl chlorides and phenylboronic acid under heterogeneous and aerobic conditions. The supported catalyst exhibited excellent activity and stability and it could be reused at least six times without any loss of activity. Atomic absorption spectroscopy detected no Pd contamination in the products, and leaching tests verified that the reaction was truly heterogeneous.
A diketiminato zinc amide complex, LZnNMe2 (1) [L = CH{(CMe)2(2,6-(i)Pr2C6H3N)2}], was prepared and investigated for the catalytic hydroamination of 2,2-dimethylpent-4-en-1-amine. The reaction with the amino olefin resulted in a transamination reaction and the subsequent insertion of the olefin moiety into the metal-amide bond. However, the reaction stopped at this point providing access to the metal alkyl intermediate, LZnR (R = N[upper bond 1 start]H-CH2-CPh2-CH2-C[upper bond 1 end]H-) (2). The isolation of this primary insertion product further strengthens the widely accepted mechanism for the intramolecular hydroamination.
The structural properties of various salts of methanetrisulfonic acid (H3mts) are described, spanning the free acid, ammonium and alkali metals (Na, K, Cs), first row transition metals (Cr, Co−Zn), and lead. A number of different coordination modes is found, including unexpected motifs such as the κ3O1,4,7 coordination in the lead salt and anions of the type [M(H2O)4(κ2O1,4‐mts)]− (M=Co, Ni, Zn), which do not seem to be persistent in aqueous solution.
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