title: Air-Stable Gold Nanoparticles Ligated by Secondary Phosphine Oxides as Catalyst for the Chemoselective Hydrogenation of Substituted Aldehydes: a Remarkable Ligand Effect.
abstract: Air-stable and homogeneous gold nanoparticles (AuNPs, 1a-5a) ligated by various secondary phosphine oxides (SPOs), [R(1)R(2)P(O)H] (R(1) = Naph, R(2) = (t)Bu, L1; R(1) = R(2) = Ph, L2; R(1) = Ph, R(2) = Naph, L3; R(1) = R(2) = Et, L4; R(1) = R(2) = Cy, L5; R(1) = R(2) = (t)Bu, 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.
authors.affiliation: †Institute of Chemical Research of Catalonia (ICIQ), 43007 Tarragona, Spain.
authors.forename: Israel
authors.initials: I
authors.lastname: Cano
authors.affiliation: †Institute of Chemical Research of Catalonia (ICIQ), 43007 Tarragona, Spain.
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Huertos
authors.affiliation: †Institute of Chemical Research of Catalonia (ICIQ), 43007 Tarragona, Spain.
authors.forename: Andrew M
authors.initials: AM
authors.lastname: Chapman
authors.affiliation: §Eduard-Zintl Institut for Inorganic and Physical Chemistry, 64287 Darmstadt, Germany.
authors.forename: Gerd
authors.initials: G
authors.lastname: Buntkowsky
authors.affiliation: §Eduard-Zintl Institut for Inorganic and Physical Chemistry, 64287 Darmstadt, Germany.
authors.forename: Torsten
authors.initials: T
authors.lastname: Gutmann
authors.affiliation: §Eduard-Zintl Institut for Inorganic and Physical Chemistry, 64287 Darmstadt, Germany.
authors.forename: Pedro B
authors.initials: PB
authors.lastname: Groszewicz
authors.affiliation: †Institute of Chemical Research of Catalonia (ICIQ), 43007 Tarragona, Spain.|‡Laboratoire de Physique et Chimie des Nano Objets, LPCNO, UMR5215 INSA-UPS-CNRS, Institut National des Sciences Appliquées, Université de Toulouse, 135 avenue de Rangueil, 31077 Toulouse, France.
authors.forename: Piet W N M
authors.initials: PW
authors.lastname: van Leeuwen