Impact of Halide (Cl vs I) Identity on the Preferred Positioning of Substituents between Al and M (M = Co, Rh, Ir) in PAlP Pincer Complexes.

Protolysis of AlMe or AlEt with 2-diisopropylphosphinopyrrole () resulted in alane/bis(phosphine) pincer ligands containing two flanking phosphines and a central Al-Me (), Al-Et () unit. Reactions of with [(COD)MI] (COD = 1,5-cyclooctadiene; M = Rh or Ir) in the presence of pyridine produced pincer complexes ( and ) with M supported by the PAlP tridentate ligand, and pyridine, methyl, and iodide as monodentate ligands for Al or M. The analogous reaction of with [(COD)MI] and pyridine resulted in the formation of the analogous compounds and with hydride in place of methyl.

Electrochemically Driven Site-Selective N-Hydroxymethylation of Indoles and Derivatives.

Described herein is a facile electrochemical strategy for the generation of formaldehyde from N,N-dimethylacetamide (DMA) and water (HO) toward a direct and site-selective N-hydroxymethylation of indoles and derivatives. Mechanistic studies suggested that N-(hydroxymethyl)-N-methylacetamide generated in situ from DMA/HO under electrochemical conditions serves as a formaldehyde surrogate. The developed methodology features mild, base- and metal catalyst-free conditions.