NC Palladacycles and C,C-chelating phosphorus ylide complexes: synthesis, X-ray characterization, and comparison of the catalytic activity in the Suzuki-Miyaura reaction
Dinuclear rhodium(I) η2:η2-cycloocta-1,5-diene (series a) and η2:η2-norborna-2,5-diene (series b) complexes with μ-RCOO- ligands, where R is linear C21H43 (complexes 1a, 1b), CH2CMe3 (2a, 2b), 1-adamantyl (3a, 3b) and benzyl (4a, 4b), have been prepared and characterized by spectroscopic methods. Structures of complexes 2b, 3a and 4a were determined by X-ray diffraction analysis. Complexes prepared show low to moderate catalytic activity in polymerization of phenylacetylene in THF giving high-cis-transoid polymers, but they show only oligomerization activity in dichloromethane.
AbstractTreatment of [(η6-p-cymene)RuCl2]2 with one equivalent of chlorodiphenylphosphine in tetrahydrofuran at reflux afforded a neutral complex [(η6-p-cymene)RuCl2(κ1-P-PPh2OH)] (1). Similarly, the reaction of [Ru(bpy)2Cl2·2H2O] (bpy = 2,2′-bipyridine) and chlorodiphenylphosphine in methanol gave a cationic complex [Ru(bpy)2Cl(κ1-P-PPh2OCH3)](PF6) (2), while treatment of [RuCl2(PPh3)3] with [2-(C5H4N)CH=N(CH2)2N(CH3)2] (L1) in tetrahydrofuran at room temperature afforded a ruthenium(II) complex [Ru(PPh3)Cl2(κ3-N,N,N-L1)] (3). Interaction of the chloro-bridged complex [Ru(CO)2Cl2]n with one equivalent of [Ph2P(o-C6H4)CH=N(CH2)2N(CH3)2] (L2) led to the isolation of [Ru(CO)Cl2(κ3-P,N,N-L2)] (4). The molecular structures of the ruthenium(II) complexes 1–4 have been determined by single-crystal X-ray crystallography. The properties of the ruthenium(II) complex 4 as a hydrogenation catalyst for acetophenone were also tested.
AbstractNanoparticles (NP) have specific catalytic properties, which are influenced by parameters like their size, shape, or composition. Bimetallic NPs, composed of two metal elements can show an improved catalytic activity compared to the monometallic NPs. We, herein, report on the selective aerobic oxidation of benzyl alcohol catalyzed by unsupported Pd/Au and Pd NPs at atmospheric pressure. NPs of varying compositions were synthesized and characterized by UV/Vis spectroscopy, transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). The NPs were tested in the model reaction regarding their catalytic activity, stability, and recyclability in batch and continuous procedure. Additionally, in situ extended X-ray absorption fine structure (EXAFS) measurements were performed in order to get insight in the process during NP catalysis.
CHELATE PHOSPHORUS YLIDE COMPLEXES OF PALLADIUM AND PLATINUM