Phosphine Ligand-Free Bimetallic Ni(0)Pd(0) Nanoparticles as a Catalyst for Facile, General, Sustainable, and Highly Selective 1,4-Reductions in Aqueous Micelles.

Phosphine ligand-free bimetallic nanoparticles (NPs) composed of Ni(0)Pd(0) catalyze highly selective 1,4-reductions of enones, enamides, enenitriles, and ketoamides under aqueous micellar conditions. A minimal amount of Pd (Ni/Pd = 25:1) is needed to prepare these NPs, which results in reductions without impacting - and -benzyl, aldehyde, nitrile, and nitro functional groups. A broad range of substrates has been studied, including a gram-scale reaction.

Shielding Effect of Nanomicelles: Stable and Catalytically Active Oxidizable Pd(0) Nanoparticle Catalyst Compatible for Cross-Couplings of Water-Sensitive Acid Chlorides in Water.

Under the shielding effect of nanomicelles, a sustainable micellar technology for the design and convenient synthesis of ligand-free oxidizable ultrasmall Pd(0) nanoparticles (NPs) and their subsequent catalytic exploration for couplings of water-sensitive acid chlorides in water is reported. A proline-derived amphiphile, PS-750-M, plays a crucial role in stabilizing these NPs, preventing their aggregation and oxidation state changes. These NPs were characterized using C nuclear magnetic resonance (NMR), infrared (IR), and surface-enhanced Raman scattering (SERS) spectroscopy to evaluate the carbonyl interactions of PS-750-M with Pd.

Metal-Micelle Cooperativity: Phosphine Ligand-Free Ultrasmall Palladium(II) Nanoparticles for Oxidative Mizoroki-Heck-type Couplings in Water at Room Temperature.

The amphiphile PS-750-M generates stable, phosphine ligand-free, and catalytically active ultrasmall Pd(II) nanoparticles (NPs) from Pd(OAc), preventing their precipitation, polymerization, and oxidation state changes. PS-750-M directly interacts with Pd(II) NP surfaces, as confirmed by high-resolution mass spectrometry and IR spectroscopy, resulting in their high stability. The Pd cations in NPs are most likely held together by hydroxides and acetate ions.

Photoassisted Charge Transfer Between DMF and Substrate: Facile and Selective N,N-Dimethylamination of Fluoroarenes.

A reversible Van der Waals complex formation between the electron-deficient fluorinated aromatic ring and N,N-dimethylformamide (DMF) molecules followed by light irradiation resulted in charge transfer (CT) process. The complex was stabilized by ammonium formate and further decomposed to form the C-N bond. Control experiments revealed that the simultaneous S Ar pathway also contributes to product formation.