14724-41-5

Upstream product

• 366-18-7 [2,2]bipyridinyl 
• 3375-31-3 palladium diacetate 
• 67-56-1 methanol 
• 172266-53-4 [Pd(Me)(1,1,1,3,3,3-hexafluoropropoxide)(2,2'-bipyridyl)] 
• 201230-82-2 carbon monoxide 
• 3375-31-3 palladium diacetate 

Downstream Products

• 73727-99-8 Pd(1,2-bis(diphenylphosphinoethane))(OCOMe)2 
• 553-90-2 Dimethyl oxalate 

Relevant academic research and scientific papers

Nanostructured Pd/C catalysts prepared by grafting of model carboxylate complexes onto functionalized carbon

Pd(5 wt%)/C catalysts were prepared by grafting carboxylate precursors onto functionalized carbon. The functionalization of the support was carried out with HNO3 or H2O2, and the number and nature of oxygenated functions introduced were determined by a combination of simplified Boehm's titration, XPS, BET, and DRIFTS. These functions were then used as anchors for model Pd precursors through covalent bonding. The underlying ligand-exchange mechanism was elucidated through detailed XPS studies. The thermal activation of the grafted materials was followed by in situ mass spectrometry, which demonstrated that it consisted of ligand losses. The activated samples were characterized by SEM, XRD, CO chemisorption, and XPS and used in the reduction of 2-methyl-2-nitropropane (MNP) into t-butylamine (TBA). The catalytic activity was shown to be correlated with the initial carbon acidity and the Pd dispersion.

Bipyridyl– and pyridylquinolyl–phenothiazine structures as potential photoactive ligands: Syntheses and complexation to palladium

Three new bipyridyl– and pyridylquinolyl–phenothiazine structures were synthesized through Pd-catalyzed C–N couplings between phenothiazine and the corresponding bromo-heteroaryls. For the 2-(N-phenothiazine)-bipyridine, boat conformation was determined for the phenothiazine moiety by X-ray diffraction analysis. Single well-defined palladium acetate complexes were observed by 1H NMR analysis with the 4-(N-phenothiazine)-bipyridine and the pyridyl-5-(N-phenothiazine)-quinoline. Compared to the naked ligands, the UV–visible absorption spectra showed, in these cases, significantly red shifted λmax upon coordination. Preliminary modeling experiments with the free and the coordinated 4-(N-phenothiazine)-bipyridine suggested for both the occurrence of electronic transfers from the phenothiazine to the bipyridine. Potentially enabling the tuning of the electron density of the coordinating moiety upon near-UV irradiation, this bipyridyl–phenothiazine structure could be the origin of a novel class of photo-active ligands for applications in organometallic catalysis.

Synthesis of 2-Alkynoates by Palladium(II)-Catalyzed Oxidative Carbonylation of Terminal Alkynes and Alcohols

A homogeneous PdIIcatalyst, utilizing a simple and inexpensive amine ligand (TMEDA), allows 2-alkynoates to be prepared in high yields by an oxidative carbonylation of terminal alkynes and alcohols. The catalyst system overcomes many of the limitations of previous palladium carbonylation catalysts. It has an increased substrate scope, avoids large excesses of alcohol substrate and uses a desirable solvent. The catalyst employs oxygen as the terminal oxidant and can be operated under safer gas mixtures.

Oxidative carbonylation of amine using water-soluble palladium catalysts in biphasic media

Application of water-soluble palladium catalysts for oxidative carbonylation of aniline to N,N′ diphenyl urea (DPU) has been reported. The water-soluble palladium catalysts prepared from sulfonated N-containing ligands were found to be highly stable under reaction conditions and easily recyclable due to insoluble urea product in the reaction medium. This is in contrast to the sulfonated phosphine ligands, which are vulnerable to oxidation under reaction conditions, showing poor activity and stability. Commercially available as well as laboratory synthesized ligands were used for preparing water-soluble palladium catalysts, for oxidative carbonylation of aniline. The best activity was obtained for Pd complex with disodium 2,2′-bipyridine-4, 4′-disulfonate (Bipy-DS) ligand. Under optimized conditions Pd(BipyDS)Pd(OAc)2 catalyst gave TOF of ～210 h-1 with aniline conversion of ～97% with ～91% selectivity for N,N′-diphenyl urea. It was found that the catalyst was easily reusable up to five times, with negligible loss in the catalytic activity. The effect of reaction parameters was investigated and a plausible reaction mechanism has been proposed.

PROCESS FOR OXIDATION OF ALKANES

A palladium complex catalyzed process for the oxidation of linear alkanes is proposed which employs molecular oxygen as the oxidant to produce secondary alcohols and ketones in high selectivity, the said catalyst is a single entity and does not requires the use of any co-catalyst or solvent.

Homogeneous palladium catalyst suppressing Pd black formation in air oxidation of alcohols

In homogeneous catalyst systems, there is the persistent problem that metal aggregation and precipitation cause catalyst decomposition and considerable loss of catalytic activity. Pd black formation is a typical example. Pd catalysts are known to easily aggregate and form Pd black, although they realize a wide variety of useful reactions in organic synthesis. In order to overcome this intrinsic problem of homogeneous Pd catalysis, we explored a new class of Pd catalyst by adopting aerobic oxidation of alcohols as a probe reaction. Herein we report a new catalyst system that suppresses the Pd black formation even under air and with a high substrate to catalyst molar ratio (S/C: more than 1000) in oxidation of alcohols. The novel pyridine derivatives having a 2,3,4,5-tetraphenylphenyl substituent and its higher dendritic unit at the 3-position of the pyridine ring were found to be excellent ligands with Pd(OAc)2 in the palladium-catalyzed air (balloon) oxidation of alcohols in toluene at 80 °C. Comparison with structurally related pyridine ligands revealed that introduction of the 2,3,4,5-tetraphenylphenyl substituent at the 3-position of pyridine ring effectively suppresses the Pd black formation, maintaining the catalytic activity for a long time to give aldehydes or ketones as products in high yields. Copyright

Carbonylation of diamino-ligated methylpalladium(II) methoxide complexes

The methylpalladium(II) methoxide complexes N)> (NN= tmeda or bpy) have been synthesized by alkoxide-methanol exchange of N) in MeOH.The bpy complex undergoes insertion of CO to give either a methyl(methoxycarbonyl) complex (at -60 deg C) or an acyl(methoxycarbonyl) complex (at - 25 deg C).Both carbonylated species were isolated and characterized at low temperature.Keywords: Palladium; Methoxycarbonyl complexes; Acyl; Carbonylation; Methoxide; Perfluoroalkoxide