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101.
A Strategy to Control the Reactivation of Frustrated Lewis Pairs from Shelf‐Stable Carbene Borane Complexes 下载免费PDF全文
Dr. Yoichi Hoshimoto Takuya Kinoshita Prof. Dr. Masato Ohashi Prof. Dr. Sensuke Ogoshi 《Angewandte Chemie (International ed. in English)》2015,54(40):11666-11671
N‐Phosphine oxide substituted imidazolylidenes (PoxIms) have been synthesized and fully characterized. These species can undergo significant changes to the spatial environment surrounding their carbene center through rotation of the phosphine oxide moiety. Either classical Lewis adducts (CLAs) or frustrated Lewis pairs (FLPs) are thus formed with B(C6F5)3 depending on the orientation of the phosphine oxide group. A strategy to reactivate FLPs from CLAs by exploiting molecular motions that are responsive to external stimuli has therefore been developed. The reactivation conditions were successfully controlled by tuning the strain in the PoxIm–B(C6F5)3 complexes so that reactivation only occurred above ambient temperature. 相似文献
102.
In the last years, the development of new methods for analyzing accurate and precise individual metalloproteins is of increasing importance, since numerous metalloproteins are excellent biomarkers of oxidative stress and diseases. In that way, methods based on the use of post column isotopic dilution analysis (IDA) or enriched protein standards are required to obtain a sufficient degree of accuracy, precision and high limits of detection. This paper reports the identification and absolute quantification of Cu,Zn-superoxide dismutase (Cu,Zn-SOD) in cytosol and mitochondria from mice hepatic cells using a innovative column switching analytical approach. The method consisted of orthogonal chromatographic systems coupled to inductively coupling plasma-mass spectrometry equipped with a octopole reaction systems (ICP-ORS-MS) and UV detectors: size exclusion fractionation (SEC) of the cytosolic and mitochondrial extracts followed by online anion exchange chromatographic (AEC) separation of Cu/Zn containing species. After purification, Cu,Zn-SOD was identified after tryptic digestion by molecular mass spectrometry (MS). The MS/MS spectrum of a doubly charged peptide was used to obtain the sequence of the protein using the MASCOT searching engine. This optimized methodology reduces the time of analysis and avoids the use of sample preconcentration and clean-up procedures, such as cut-off centrifuged filters, solid phase extraction (SPE), precipitation procedures, off-line fractions insolates, etc. In this sense, the method is robust, reliable and fast with typical chromatographic run time less than 20 min. Precision in terms of relative standard deviation (n = 5) is of 3–5% and detection limits is 0.21 ng Cu g−1. 相似文献
103.
Nina K. GusarovaPavel A. Volkov Nina I. IvanovaLudmila I. Larina Boris A. Trofimov 《Tetrahedron letters》2011,52(18):2367-2369
The multi-component reaction between secondary phosphine selenides and amines (primary, secondary, and primary diamines) proceeds using the Et3N-CCl4 system under mild conditions to give phosphinoselenoic amides or diamides in 81-89% isolated yields. 相似文献
104.
评价了一种碳水化合物衍生的具有较大立体位阻及较三苯基膦更富电子的膦配体(甲基3-脱氧-3-二苯膦基-4,6-氧-苯次甲基-α-D-吡喃阿卓糖苷,3-MBPA)在Pd催化的Heck反应中的性能.发现在N,N-二甲基乙酰胺溶刺中K2CO3是该催化体系较适合的碱;在该配体的支持下催化剂中钯的用量可低至0.5 mo1%;可催化苯乙烯与带给电子基团的溴代芳烃及带吸电子基团的氯代芳烃发生反应,高产率地生成相应的偶联产物;反应区域选择性表明,Pd(OAc)2/3-MBPA体系在催化苯乙烯与卤代芳烃的Heck反心中并存阳离子催化途径,说明3-MBPA中的氧原了可能也参与配位;同时发现,加入助配体四丁基溴化胺(TBAB)后,可能是Br-参与配位有利于增加中性催化途径的机会而提高了反应区域选择性. 相似文献
105.
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107.
Han C Xie G Li J Zhang Z Xu H Deng Z Zhao Y Yan P Liu S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(32):8947-8956
An efficient host for blue and green electrophosphorescence, 4,6‐bis(diphenylphosphoryl)dibenzofuran ( o‐ DBFDPO ), with the structure of a short‐axis‐substituted dibenzofuran was designed and synthesised. It appears that the greater density of the diphenylphosphine oxide (DPPO) moieties in the short‐axis substitution configuration effectively restrains the intermolecular interactions, because only very weak π–π stacking interactions could be observed, with a centroid‐to‐centroid distance of 3.960 Å. The improved thermal stability of o‐ DBFDPO was corroborated by its very high glass transition temperature (Tg) of 191 °C, which is the result of the symmetric disubstitution structure. Photophysical investigation showed o‐ DBFDPO to be superior to the monosubstituted derivative, with a longer lifetime (1.95 ns) and a higher photoluminescent quantum efficiency (61 %). The lower first singlet state excited level (3.63 eV) of o‐ DBFDPO demonstrates the stronger polarisation effect attributable to the greater number of DPPO moieties. Simultaneously, an extremely high first triplet state excited level (T1) of 3.16 eV is observed, demonstrating the tiny influence of short‐axis substitution on T1. The improved carrier injection ability, which contributed to low driving voltages of blue‐ and green‐emitting phosphorescent organic light‐emitting diodes (PHOLEDs), was further confirmed by Gaussian calculation. Furthermore, the better thermal and morphological properties of o ‐DBFDPO and the matched frontier molecular orbital (FMO) levels in the devices significantly reduced efficiency roll‐offs. Efficient blue and green electrophosphorescence based on the o ‐DBFDPO host was demonstrated. 相似文献
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109.
Giovanni Ricci Giuseppe Leone Giorgia Zanchin Benedetta Palucci Alessandra Forni Anna Sommazzi Francesco Masi Stefano Zacchini Massimo Guelfi Guido Pampaloni 《Molecules (Basel, Switzerland)》2021,26(13)
Some novel cobalt diphenylphosphine complexes were synthesized by reacting cobalt(II) chloride with (2-methoxyethyl)diphenylphosphine, (2-methoxyphenyl)diphenylphosphine, and 2-(1,1-dimethylpropyl)-6-(diphenylphosphino)pyridine. Single crystals suitable for X-ray diffraction studies were obtained for the first two complexes, and their crystal structure was determined. The novel compounds were then used in association with methylaluminoxane (MAO) for the polymerization of 1,3-butadiene, and their behavior was compared with that exhibited in the polymerization of the same monomer by the systems CoCl2(PnPrPh2)2/MAO and CoCl2(PPh3)2/MAO. Some significant differences were observed depending on the MAO/Co ratio used, and a plausible interpretation for such a different behavior is proposed. 相似文献
110.
Adeline Leyris 《Tetrahedron letters》2005,46(50):8677-8680
Both enantiomers of tert-butylphenylphosphine oxide can be easily synthesised starting from (S)-prolinol-based oxazaphospholidine. 相似文献