Air-Stable Gold Nanoparticles Ligated by Secondary Phosphine Oxides as Catalyst for the Chemoselective Hydrogenation of Substituted Aldehydes: a Remarkable Ligand Effect - CNRS - Centre national de la recherche scientifique Accéder directement au contenu
Article Dans Une Revue Journal of the American Chemical Society Année : 2015

Air-Stable Gold Nanoparticles Ligated by Secondary Phosphine Oxides as Catalyst for the Chemoselective Hydrogenation of Substituted Aldehydes: a Remarkable Ligand Effect

Résumé

Air-stable and homogeneous gold nanoparticles (AuNPs, 1a–5a) ligated by various secondary phosphine oxides (SPOs), [R1R2P(O)H] (R1 = Naph, R2 = tBu, L1; R1 = R2 = Ph, L2; R1 = Ph, R2 = Naph, L3; R1 = R2 = Et, L4; R1 = R2 = Cy, L5; R1 = R2 = tBu, L6), with different electronic and steric properties were synthesized via NaBH4 reduction of the corresponding Au(I)–SPO complex. These easily accessible ligands allow the formation of well dispersed and small nanoparticles (size 1.2–2.2 nm), which were characterized by the use of a wide variety of techniques, such as transmission electron microscopy, thermogravimetric analysis, UV–vis, energy-dispersive X-ray, X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR FT-IR), and cross polarization magic angle spinning (CP MAS) NMR spectroscopy. A pronounced ligand effect was found, and CP MAS NMR experiments enabled us to probe important differences in the polarity of the P–O bond of the SPOs coordinated to the nanoparticle surface depending on the type of substituents in the ligand. AuNPs containing aryl SPOs carry only SPO anions and are highly selective for aldehyde hydrogenation. AuNPs of similar size made with alkyl SPOs contain also SPOH, hydrogen bonded to SPO anions. As a consequence they contain less Au(I) and more Au(0), as is also evidenced by XPS. They are less selective and active in aldehyde hydrogenation and now show the typical activity of Au(0)NPs in nitro group hydrogenation.

Domaines

Chimie
Fichier non déposé

Dates et versions

hal-02018762 , version 1 (14-02-2019)

Identifiants

  • HAL Id : hal-02018762 , version 1

Citer

Israel Cano, Miguel Huertos, Andrew Chapman, Gerd Buntkowsky, Torsten Gutmann, et al.. Air-Stable Gold Nanoparticles Ligated by Secondary Phosphine Oxides as Catalyst for the Chemoselective Hydrogenation of Substituted Aldehydes: a Remarkable Ligand Effect. Journal of the American Chemical Society, 2015, 137 (24), pp.7718-7727. ⟨hal-02018762⟩
66 Consultations
0 Téléchargements

Partager

Gmail Facebook X LinkedIn More