87573-07-7Relevant articles and documents
Benzoato and thiobenzoato ligands in the synthesis of dinuclear palladium(III) and -(II) compounds: Stability and catalytic applications
Estevan, Francisco,Ibá?ez, Susana,Ofori, Albert,Hirva, Pipsa,Sanaú, Mercedes,úbeda, Ma Angeles
, p. 2822 - 2832 (2015)
New palladium(III) compounds of formula Pd2[(C6H4)PPh2]2[OXC(C6H5)]2Cl2 [3a (X = O); 3b (X = S)] were obtained by the oxidation of the analogous palladium(II) ones with PhICl2 and were characterized by 31P, 1H, and 13C NMR spectroscopy at 223 K. Compound 3a was also structurally characterized by single-crystal X-ray diffraction methods, which revealed a Pd-Pd distance of 2.5212(10) ?. DFT calculations were conducted to study the stability of all of these new palladium(III) and -(II) compounds with focus on the influence of the O虠S substitution of the donor atom in the ligand. The palladium(II) compounds Pd2[(C6H4)PPh2]2[OXC(C6H5)]2 [2a (X = O), 2b (X = S)] were also tested as precatalyst in two reactions: (1) the acetoxylation of 2-phenylpyridine and (2) the room-temperature 2-phenylation of indoles. Compound 2b is a better precatalyst than 2a in the first reaction (4 h; isolated yield, 67.5 vs. 50.4 %). In the second catalytic reaction, isolated yields of 97 (10 h, substrate: 1-methylindole) and 99 % (24 h, substrate: indole) were obtained with 2a as the precatalyst, whereas 2b gave low or no conversion. Dinuclear palladium(III) and -(II) compounds with benzoato and thiobenzoato ligands are synthesized. DFT calculations are performed to study the stability of these compounds and the influence of the O虠S substitution of the donor atom. The catalytic activity of the palladium(II) complexes is also tested in the acetoxylation of 2-phenylpyridine and the room-temperature 2-phenylation of indoles.
Hypercrosslinked Polymer Platform-Anchored Single-Site Heterogeneous Pd-NHC Catalysts for Diverse C-H Functionalization
Mandal, Tanmoy,Mondal, Moumita,Choudhury, Joyanta
supporting information, p. 2443 - 2449 (2021/08/03)
We demonstrate a new class of hypercrosslinked polymer (HCP) platform-Anchored single-site heterogenized Pd-NHC catalysts for multipurpose C-H functionalization reactions. This new class is represented by a set of three catalysts, viz., HCP-B-MeNHC-Pd, HCP-B-BnNHC-Pd, and HCP-TPM-MeNHC-Pd, having a variation on the structural feature of the anchoring polymeric platform. All three catalysts were fully characterized via diverse solid-state characterization and analytical techniques such as X-ray photoelectron spectroscopy, 13C cross-polarization magic-Angle-spinning nuclear magnetic resonance, field-emission scanning electron microscopy, energy-dispersive X-ray analysis, thermogravimetric analysis, and inductively coupled plasma-optical emission spectrometry. Three types of regularly practiced and very useful C-H functionalization reactions, viz., C-H halogenation, acetoxylation, and arylation, are tested with the new catalysts and found to be highly compatible and successful. With the HCP-TPM-MeNHC-Pd catalyst, up to 85, 75, and 70% yields of the functionalized products were achieved for the halogenation, acetoxylation, and arylation reactions, respectively. Demanding attributes such as enhanced activity, heterogeneity, and recyclability are offered by this new system, making it a promising candidate in the field of heterogeneous C-H functionalization, where only a few efficient catalysts are available.
Directed Aromatic C-H Activation/Acetoxylation Catalyzed by Pd Nanoparticles Supported on Graphene Oxide
Zhang, Yi,Zhao, Yu,Luo, Yu,Xiao, Liuqing,Huang, Yuxing,Li, Xingrong,Peng, Qitao,Liu, Yizhen,Yang, Bo,Zhu, Caizhen,Zhou, Xuechang,Zhang, Junmin
supporting information, p. 6470 - 6473 (2017/12/26)
The first solid-supported directed aromatic C-H activation/acetoxylation has been successfully developed by using palladium nanoparticles supported on graphene oxide (PdNPs/GO) as a catalyst. The practicability of this method is demonstrated by simple preparation of catalyst, high catalytic efficiency, wide functional group tolerance, and easy scale up of the reaction. A hot filtration test and Hg(0) poisoning test indicate the heterogeneous nature of the catalytic active species.
