2052-07-5Relevant articles and documents
Ferrocenylated imine- and amine(secondary/tertiary)- phosphine P^N ligands and their Pd(II) complexes: Synthesis and structural characterization
Anzaldo, Bertin,Gavi?o, Ruben,Gutiérrez, René,Sharma, Pankaj,Toscano, Alfredo R.,Villamizar C, Claudia P.
, (2020)
A new family of ferrocenylated P^N ligands where the nitrogen donor is either of an imine or amine (secondary/tertiary), was synthesized. The condensation reaction between diphenylphosphino propylamine and formyl ferrocene led to the formation of imine ligand [(η5-C5H5)Fe{(η5-C5H4)CH=N-(CH2)3-PPh2)}] (1), which on reduction with NaBH4 gave secondary amine ligand [(η5-C5H5)Fe{(η5-C5H4)CH2-NH-(CH2)3-PPh2)}] (2). Additionally, nucleophilic substitution reaction of diphenylphosphino ethyl/propyl amine with [FcCH2NMe3+][I?] salt leads to tertiary-amine ligand [(η5-C5H5)Fe(η5-C5H4)CH2]2-N-(R-PPh2) where R= C2H4 (3) and C3H6 (4). The newly synthesized ferrocenylated ligands were then complexed with Pd(II) giving [cis(κ2-P^N)PdCl2] type complexes (5-8), where imine, secondary amine, and tertiary amine ligands act as a bidentate ligand. The molecular structures of ligand (3), and complexes (5), (6), and (7) have also been determined by X-ray crystallography. In the molecular structures of these complexes, the Pd(II) center presents a distorted square-planar geometry. During the isolation of ligand (4), corresponding phosphine oxide (4A) along with a phosphonium salt (4B) was also isolated as by-products and were characterized by X-ray crystallography. The preliminary catalytic evaluation of complex (7) in the Suzuki-Miyaura cross-coupling reaction of arylboronic acids with aryl bromides was performed.
Ferrocene-Labeled Carbon-Encapsulated Iron Nanoparticles: The First Magnetic Nanocatalysts for C-H Arylation toward 1,1′-Biphenyl Formation
Kasprzak, Artur,Bystrzejewski, Michal,Poplawska, Magdalena
, p. 409 - 415 (2019)
The first magnetic nanocatalysts for C-H arylation toward 1,1′-biphenyl formation are described. The nanocatalysts are based on conjugates of ferrocene and carbon-encapsulated iron nanoparticles. The highest catalytic activity was found for ferrocene conjugated to carbon-encapsulated iron nanoparticles via the N-methylpyrrolidine moiety. In the presence of the nanocatalyst, various 1,1′-biphenyls can be obtained in high yields (84-90%). The effect of substitution of the aniline's phenyl ring on the reaction yield is also included in this work. The nanocatalyst can be easily separated from the reaction mixture and can be reused in up to four reaction cycles without any loss of its high catalytic activity. Our work sheds light on a potential application of functionalized carbon-encapsulated iron nanoparticles in modern industrial organic processes toward more economical manufacturing of organic compounds.
Morphology control of nanofibril donor-acceptor heterojunction to achieve high photoconductivity: Exploration of new molecular design rule
Huang, Helin,Chou, Ching-En,Che, Yanke,Li, Ligui,Wang, Chen,Yang, Xiaomei,Peng, Zhonghua,Zang, Ling
, p. 16490 - 16496 (2013)
Donor-acceptor nanofibril composites have been fabricated, and the dependence of their photocurrent response on the structure and morphology of the donor part has been systematically investigated. The nanofibril composites were composed of template nanofibers, assembled from an electron acceptor molecule, perylene tetracarboxylic diimide (PTCDI), onto which (through drop-casting) various electron donor molecules (D1-D4) were coated. The donor molecules have the same π-conjugated core, but different side groups. Due to the different side groups, the four donor molecules showed distinctly different propensity for intermolecular aggregation, with D1-D3 forming segregated phases, while D4 prefers homogeneous molecular distribution within the film. It was found that the nanofibril composites with D4 exhibit the highest photocurrent, whereas those with aggregation-prone D1-D3 exhibited much lower photocurrent under the same illumination condition. Solvent annealing is found to further enhance the aggregation of D1-D3 but facilitate more uniform molecular distribution of D4 molecules. As a result, the photocurrent response of PTCDI fibers coated with D1-D3 decreased after vapor annealing, whereas those coated with D4 further increased. The detrimental effect of the aggregation of donor molecules on the PTCDI fiber is likely due to the enhanced local electrical field built up by the high charge density around the aggregate-nanofiber interface, which hinders the charge separation of the photogenerated electron-hole pair. The results reported in this study give further insight into the molecular structural effect on photoconductivity of hybrid materials, particularly those based on donor-acceptor composites or interfaces, and provide new molecular design rules and material processing guidelines to achieve high photoconductivity.
Functionalized Phosphonium Ionic Liquids: Synthesis and Application
Arkhipova, Daria,Ermolaev, Vadim,Miluykov, Vasili,Nigmatullina, Lilia,Sinyashin, Oleg
, p. 899 - 901 (2015)
A series of phosphonium salts with sterically hindered cation But3P+(CH2COOEt)X- (X = Cl, BF4, N(SO2CF3)2) (1) was prepared for the first time. Palladium nanoparticles (PdNPs) stabilized by (1) showed moderate activity as catalyst in Suzuki cross-coupling reaction of bromoarenes and phenylboronic acid.
METHOD FOR PRODUCING HALOGEN COMPOUND
-
Paragraph 0054-0060; 0069-0071; 0091-0093, (2021/09/29)
PROBLEM TO BE SOLVED: To provide a method for efficiently producing an aromatic compound containing a halogen group(s). SOLUTION: Provided is a method for producing a halogen compound represented by the following general formula (1), comprising reacting an iodine compound represented by the following general formula (2) and a compound represented by the following general formula (3) in the presence of a transition metal compound, at least one phosphine compound selected from the group consisting of 1,1'-bis(diphenylphosphino)ferrocene and 4,5'-bis(diphenylphosphino)-9,9'-dimethylxanthene, and a base. (In the formula, Ar1 and Ar2 each independently represent a C1-40 organic group; X represents a bromine group, a chlorine group, a fluorine group, or a trifluoromethanesulfonate group, and when there are a plurality of X's, they may be the same or different; n represents an integer equal to or larger than 1; R's each independently represent a hydrogen atom, a C1-4 alkyl group, or a phenyl group, and two R's may be linked to form a ring containing oxygen atoms and a boron atom.) SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
Benchtop-Stabssle Hypervalent Bromine(III) Compounds: Versatile Strategy and Platform for Air- And Moisture-Stable λ3-Bromanes
Miyamoto, Kazunori,Saito, Motomichi,Tsuji, Shunsuke,Takagi, Taisei,Shiro, Motoo,Uchiyama, Masanobu,Ochiai, Masahito
, p. 9327 - 9331 (2021/07/01)
We present the first synthesis of air/moisture-stable λ3-bromanes (9and10) by using a cyclic 1,2-benzbromoxol-3-one (BBX) strategy. X-ray crystallography and NMR and IR spectroscopy ofN-triflylimino-λ3-bromane (12) revealed that the bromine(III) center is effectively stabilized by intramolecular R-Br-O hypervalent bonding. This strategy enables the synthesis of a variety of air-, moisture-, and benchtop-stable Br-hydroxy, -acetoxy, -alkynyl, -aryl, and bis[(trifluoromethyl)sulfonyl]methylide λ3-bromane derivatives.
Palladium-catalyzed relay C–H functionalization to construct novel hybrid-arylcyclophosphorus ligand precursors
Bai, Peng-Bo,Wang, Juan,Yang, Shang-Dong
supporting information, (2021/11/17)
A new relay C–H functionalization of di([1,1′-biphenyl]-2-yl)phosphine oxide to obtain esterified and hydroxylated products with different hypervalent iodines as oxidants under palladium catalysis is disclosed. This reaction provides a more effective and concise strategy for the synthesis of novel structural hybrid-arylcyclophosphorus ligand precursors with a wide range of substrates and good functional group tolerance.
Synthesis of Dibenzosiloles through Electrocatalytic Sila-Friedel-Crafts Reaction
Han, Pan,Yin, Mengyun,Li, Haiqiong,Yi, Jundan,Jing, Linhai,Wei, Bangguo
supporting information, p. 2757 - 2761 (2021/04/16)
A novel electrocatalyzed method for the preparation of dibenzosiloles was developed through intramolecular C?H/Si?H dehydrogenative coupling strategy starting from biarylhydrosilanes. Both electro-donating and electro-withdrawing substitution groups were tolerated for this transformation, and the desired dibenzosilole products could be obtained in moderate to excellent yields. A sila-Friedel-Crafts reaction mechanism was proposed on the basis of previous literature and our controlled experiments. (Figure presented.).
Rh(III)-Catalyzed Annulation of 2-Biphenylboronic Acid with Diverse Activated Alkenes
Chang, Junbiao,Dong, Zhenzhen,Li, Xingwei,Liu, Bingxian,Yang, Lingyun
supporting information, p. 7199 - 7204 (2021/09/22)
Rhodium(III)-catalyzed annulation of 2-biphenylboronic acids with three classes of activated alkenes has been realized, leading to the synthesis of fused or bridged cyclic skeletons via transmetalation-initiated C-H activation. In the annulative coupling of 2-biphenylboronic acid with a CF3-substituted enone, the bulky cyclopentadienyl ligand (CptBu) in the catalyst proved effective to promote the reductive elimination process prior to protonolysis, affording the [4 + 2] annulated products instead of the simple 1,4-addition product. Seven-membered rings were obtained when disubstituted cyclopropenones were employed. Bridged cycles were isolated from the coupling of 2-biphenylboronic acid with benzoquinones as a result of 2-fold Michael additions. The substrate scopes were found to be broad with up to 99% yield under air-tolerant conditions.
A ferrocene-templated Pd-bearing molecular reactor
Gunka, Piotr A.,Kasprzak, Artur
supporting information, p. 6974 - 6979 (2020/06/04)
High-yield, chromatography-free syntheses of a ferrocene-templated molecular cage and its Pd-bearing derivative are presented. The formation of a symmetric cage-type structure was confirmed by single-crystal X-ray diffraction analysis. The Pd-bearing cage was used as an innovative catalyst for the efficient synthesis of 1,1'-biphenyls under mild conditions. The presented catalyst is reusable and 1,1'-biphenyls can be obtained efficiently in a gram scale process.
