75732-01-3Relevant articles and documents
Synthesis and Reactivity of Fluoroalkyl Copper Complexes by the Oxycupration of Tetrafluoroethylene
Ohashi, Masato,Adachi, Takuya,Ishida, Naoyoshi,Kikushima, Kotaro,Ogoshi, Sensuke
, (2017)
The copper(I)-mediated generation of -OCF2CF2- moieties by the oxycupration of tetrafluoroethylene (TFE) using either copper aryloxides or alkoxides is disclosed. The key intermediates, 2-aryloxy-1,1,2,2-tetrafluoroethyl and 2-alkoxy
Binuclear β-diketiminate complexes of copper(i)
Phanopoulos, Andreas,Leung, Alice H. M.,Yow, Shuhui,Palomas, David,White, Andrew J. P.,Hellgardt, Klaus,Horton, Andrew,Crimmin, Mark R.
supporting information, p. 2081 - 2090 (2017/02/23)
The reaction of a series of dinucleating bis(β-diketiminate) pro-ligands with mesitylcopper in the presence and absence of mono and diphosphines has allowed the isolation of a new series of dicopper(i) complexes. Inclusion of trans-1,2-cyclohexyl (1), 2,6-pyridyl (2), and 2,2′-oxydiaryl (3) spacers between the β-diketiminate units has been studied. The isolation of three new copper(i) phosphine complexes [1·Cu2(PPh3)2], [2·Cu2(PPh3)2] and [3·Cu2(PPh3)2] is reported. While these compounds display large Cu?Cu separations of 5.4-7.9 ? in the solid state, solution data are consistent with a large degree of conformational freedom. Modification of the monophosphine to a diphosphine, DPPE, allowed the isolation of the novel 11-membered bimetallic macrocycle [2·Cu2(DPPE)] containing both a binucleating nitrogen based ligand and a chelating diphosphine. While acetonitrile adducts of this series could also be generated in situ, under forcing conditions reaction of the 2,6-pyridyl bridged ligand with mesityl copper led to the formation [2·Cu2]2. This latter complex is a dimer of dicopper(i) units in which the bis(β-diketiminate) ligand now binds four copper(i) centers through not only the expected κ2-N,N′-chelation but also κ1- and η2-binding of the central pyridine through orthogonal Cu-N and Cu-arene interactions. Reversible coordination of alkenes, pyridine and quinoline to the copper cluster was identified allowing the isolation and structural characterisation of a further series of dinuclear complexes [2·Cu2(pyridine)2], [2·Cu2(cyclopentene)2] and [2·Cu2(norbornene)2]. Solution studies allow quantification of the reversible binding event through a van't Hoff analysis. Both solution and the solid state data suggest a weak anagostic interaction exists in the latter two alkene complexes of copper(i). The new complexes have been characterized by X-ray diffraction, multinuclear NMR spectroscopy and CHN analysis.
Enantioselective Borylative Dearomatization of Indoles through Copper(I) Catalysis
Kubota, Koji,Hayama, Keiichi,Iwamoto, Hiroaki,Ito, Hajime
supporting information, p. 8809 - 8813 (2015/11/27)
The enantioselective borylative dearomatization of a heteroaromatic compound has been achieved using a copper(I) catalyst and a diboron reagent. This reaction involves the regio- and enantioselective addition of active borylcopper(I) species to indole-2-carboxylates, followed by the diastereoselective protonation of the resulting copper(I) enolate to give the corresponding chiral indolines, which bear consecutive stereogenic centers.
Porphyrinylboranes Synthesized via Porphyrinyllithiums
Fujimoto, Keisuke,Yorimitsu, Hideki,Osuka, Atsuhiro
supporting information, p. 11311 - 11314 (2015/08/03)
As the most nucleophilic porphyrins, meso- or β-lithiated porphyrins were generated by iodine-lithium exchange reactions of the corresponding iodoporphyrins with n-butyllithium at -98°C. Porphyrinyllithiums thus prepared were used for synthesis of dimesitylporphyrinylboranes through reactions with fluorodimesitylborane. The boryl groups proved to serve as an electron-accepting unit to alter the photophysical and electrochemical properties. In addition, 5-diarylamino-15-dimesitylboryl-substituted donor-accepter porphyrins showed increased intramolecular charge-transfer character in the S1 state. Furthermore, the reaction of β-lithiated porphyrin with dichloromesitylborane provided a boron-bridged porphyrin dimer, which exhibited a conjugative interaction between two porphyrin units through the vacant p-orbital on the boron center. Porphyrinyllithiums were generated by iodine-lithium exchange of the corresponding iodoporphyrins. The porphyrinyllithiums were useful for the synthesis of a series of porphyrinylboranes through reactions with suitable haloboranes. The boryl groups served as electron-accepting units to alter the photophysical and electrochemical properties. A B,N-substituted donor-accepter porphyrin showed an increased intramolecular charge-transfer character in the S1 state. A boron-bridged porphyrin dimer exhibited a conjugative interaction between two porphyrin units through the vacant p-orbital at the boron atom.
Isolation and X-ray crystal structures of triarylphosphine radical cations
Pan, Xiaobo,Chen, Xiaoyu,Li, Tao,Li, Yizhi,Wang, Xinping
supporting information, p. 3414 - 3417 (2013/04/23)
Salts containing triarylphosphine radical cations 1?+ and 2?+ have been isolated and characterized by electron paramagnetic resonance (EPR) and UV-vis absorption spectroscopy as well as single-crystal X-ray diffraction. Radical 1?+ exhibits a relaxed pyramidal geometry, while radical 2?+ becomes fully planar. EPR studies and theoretical calculations showed that the introduction of bulky aryl groups leads to enhanced p character of the singly occupied molecular orbital, and the radicals become less pyramidalized or fully flattened.
