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71.
Dr. Thies Olaf Petersen Dustin Simone Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(44):15847-15855
Attempts to prepare previously unknown simple and very Lewis acidic [RZn]+[Al(ORF)4]? salts from ZnR2, AlR3, and HO?RF delivered the ion‐like RZn(Al(ORF)4) (R=Me, Et; RF=C(CF3)3) with a coordinated counterion, but never the ionic compound. Increasing the steric bulk in RZn+ to R=CH2CMe3, CH2SiMe3, or Cp*, thus attempting to induce ionization, failed and led only to reaction mixtures including anion decomposition. However, ionization of the ion‐like EtZn(Al(ORF)4) compound with arenes yielded the [EtZn(arene)2]+[Al(ORF)4]? salts with arene=toluene, mesitylene, or o‐difluorobenzene (o‐DFB)/toluene. In contrast to the ion‐like EtZn(η3‐C6H6)(CHB11Cl11), which co‐crystallizes with one benzene molecule, the less coordinating nature of the [Al(ORF)4]? anion allowed the ionization and preparation of the purely organometallic [EtZn(arene)2]+ cation. These stable materials have further applications as, for example, initiators of isobutene polymerization. DFT calculations to compare the Lewis acidities of the zinc cations to those of a large number of organometallic cations were performed on the basis of fluoride ion affinity. The complexation energetics of EtZn+ with arenes and THF was assessed and related to the experiments. 相似文献
72.
Mutsuo Igarashi 《Molecular Crystals and Liquid Crystals》2013,570(2):437-440
Abstract Spin-spin relaxation of 23Na-NMR is observed by the spin echo method at room temperature for Y-type zeolite loaded with Na metal without hydration. For saturated and no levels of loading, the echo decay is well fitted by single exponential function. T 2 decreases to be 0.25 times smaller by loading. This decrease of T 2 is explained semiquantitatively with assuming nuclear dipole-dipole interaction between neighboring Na. 相似文献
73.
Dr. Agnes Kütt Prof. Dr. Gunnar Jeschke Dr. Lauri Toom Dr. Jaak Nerut Prof. Christopher A. Reed 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(41):8871-8874
Hydride abstraction from diarylamines with the trityl ion is explored in an attempt to generate a stable diarylnitrenium ion, Ar2N+. Sequential H-atom abstraction reactions ensue. The first H-atom abstraction leads to intensely colored aminium radical cations, Ar2NH.+, some of which are quite stable. However, most undergo a second H-atom abstraction leading to ammonium ions, Ar2NH2+. In the absence of a ready source of H-atoms, a unique self-abstraction reaction occurs when Ar=Me5C6, leading to a novel iminium radical cation, Ar=N.+Ar, which decays via a second self H-atom abstraction reaction to give a stable iminium ion, Ar=N+HAr. These products differ substantially from those derived via photochemically produced diarylnitrenium ions. 相似文献
74.
《Tetrahedron letters》2014,55(50):6895-6898
A new dimethylsulfoxide activation method employing 1,1-dichlorocycloheptatriene has been developed for a mild Swern-type oxidation of a variety of alcohols. The carbonyl products can be obtained in good to excellent yields from this operationally simple and efficient method. This work is the first report of dimethylsulfoxide activation by a simple chlorinated hydrocarbon reagent, which has the unique ability of equilibrating to its reactive aromatic cationic form. 相似文献
75.
76.
Fahmy M. Asaad Nazih Latif Nawal Mishriky Ibrahim Zeid 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):17-18
Abstract In the present investigation, the authors could obtain a new series of spiranes (1) through the reaction of the high potential quinone tetrachloro-o-benzoquinone with 2-aryl-3-phenyl-3H-quinazoline-4-thiones. Thus, 2,3-diphenyl- (2a), 2-p-tolyl-3-phenyl- (2b) and 2-p-anisyl-3-phenyl- (2c)-3H-quinazoline-4-thiones react readily with tetrachloro-o-benzoquinone, in boiling toluene, to give the corresponding spiro-1,3-benzodioxole-2,4′-(3′H)-quinazolines (1a-c), respectively. 相似文献
77.
78.
Vadapalli Chandrasekhar Viswanathan Baskar Ramamoorthy Boomishankar Selvarajan Nagendran 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4-5):699-701
The reactions of n-butyl stannonic acid with(PhO) 2 P(O)H leads to the formation of a hexameric tin cage [{(n-BuSn) 3 (PhO) 3 O} 2 {HPO 3 } 4 ].This reaction involves an in situ P─O bond cleavage and the generation of a [HPO 3 ] 2? ion. A direct reaction of six equivalents of n-BuSnO(OH) acid with six equivalents of C 6 H 5 OH and four equivalents of H 3 PO 3 also leads to the formation of same cage structure. A tetranuclear organooxotin cage[(PhCH 2 ) 2 Sn 2 O(O 2 P(OH)-t-Bu) 4 ] 2 has been assembled by debenzylation involving the reaction of (PhCH 2 ) 2 SnCl 2 ,(PhCH 2 ) 2 SnO·H 2 O or (PhCH 2 ) 3 SnCl with two equivalents of t-BuP(O)OH 2 . A half-cage intermediate [(PhCH 2 ) 2 Sn 2 O(O 2 P(OH)-t-Bu) 4 ] has been detected. New organotin cations of the type [n-Bu 2 Sn(H 2 O) 4 ] 2+[2,5-Me 2 -C 6 H 3 SO 3 ]? 2 and {[n-Bu 2 Sn(H 2 O) 3 LSn(H 2 O) 3 (n-Bu) 2 ] 2+[1,5-(SO 3 ) 2 -C 10 H 6 ] 2?} have been obtained in the reactions of n-Bu 2 SnO or (n-Bu 3 Sn) 3 O with 2,5-dimethyl sulfonic acid and 1,5-naphthalene disulfonic acid respectively. These organotin cations form interesting supramolecular structures in the solid state as a result of O─H─···O hydrogen bonding. 相似文献
79.
Nives Galić Nataša Burić Renato Tomaš Leo Frkanec Vladislav Tomišić 《Supramolecular chemistry》2013,25(5):389-397
The fluorescent peptidocalixarenes, 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(O-methyl-l-tryptophanylcarbonylmethoxy)calix[4]arene (1) and 5,11,17,23-tetra-tert-butyl-25,27-di(O-methyl)-26,28-bis(O-methyl-l-tryptophanylcarbonylmethoxy)calix[4]arene (2), were prepared by introducing tryptophan subunits at a lower calixarene rim. Coordination abilities of 1 and 2 towards Eu(III) and alkali metal cations were studied by spectrophotometric, spectrofluorimetric, conductometric and potentiometric titrations in acetonitrile at 25°C. Rather strong complexation was observed for smaller alkali metal cations Li+ and Na+ (log K Li1 >6, log K Li2 >6, log K Na1 = 8.25, log K Na2 = 6.94), and moderate for K+ (log K K1 = 5.09, log K K2 = 4.09). Larger Rb+ and Cs+ cations did not fit in the ion binding site of 1 so no complexation was detected, whereas the more flexible ligand 2 accommodated Rb+ cation (log K Rb2 = 3.44). The fluorescence of 1 (λex = 280 nm, λem = 340 nm) was remarkably quenched by Eu(III). Stability constant of 1:1 (Eu3+:1) complex determined spectrofluorimetrically amounted to log K Eu1 = 6.16. 相似文献
80.
Francine F. Nachtigall Eduardo Ernesto Castellano Faruk Nome 《Supramolecular chemistry》2013,25(6):453-458
The interactions of calix[6]arene and p-tert-butylcalix[6]arene with aliphatic amines in acetonitrile solution were studied by spectrophotometric titrations in the UV region and 1H NMR spectrometry. Calix[6]arenes can undergo two deprotonations by aliphatic amines and the extent of the second proton transfer is mainly governed by the size of the α-substituent of the amine. 1H NMR spectra show that the macrocycle adopts a 1,2,3-alternate conformation and that the α-hydrogens of the ammonium ions are shielded by the π-clouds of the aromatic rings. The X-ray crystal structure of the dihexylammonium complex of the p-tert-butylcalix[6]arene dianion, reported here, confirms the 1,2,3-alternate conformation and shows one of the two ammonium moieties encapsulated in the inner cavity of the macrocycle. 相似文献