排序方式: 共有71条查询结果,搜索用时 31 毫秒
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Rostovtsev VV Bryman LM Junk CP Harmer MA Carcani LG 《The Journal of organic chemistry》2008,73(2):711-714
We have recently developed an improved synthetic route to 1,1,2,2-tetrafluoroethanesulfonic acid (HCF2CF2SO3H, TFESA) and explored the applications of this newly available superacid in catalysis. Low volatility, ease of handling, and a convenient 1H NMR handle make this acid an attractive alternative to triflic acid. TFESA can also be converted to several of its derivatives: anhydride, sulfonyl chloride, and sulfonyl fluoride, which provide a good entry point for the synthesis of aryl sulfonates. We prepared several aryl esters of 1,1,2,2-tetrafluoroethanesulfonic acid (aryl tetraflates) and showed that they can be used in a number of palladium-catalyzed coupling reactions (Suzuki, Heck, and Buchwald-Hartwig couplings). While the reactivity of tetraflates lies between that of triflates and chlorides, tetraflates appear to be more thermally stable. Additionally, the presence of a hydrogen atom in the tetraflate group facilitates monitoring of reactions and characterization of derivatives. 相似文献
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Bolm C Martin M Gescheidt G Palivan C Stanoeva T Bertagnolli H Feth M Schweiger A Mitrikas G Harmer J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(6):1842-1850
The initial steps of an enantioselective Diels-Alder reaction catalyzed by a CuII-bissulfoximine complex were followed by EXAFS (EXAFS=extended X-ray absorption fine structure), EPR (EPR=electron paramagnetic resonance) spectroscopy (CW-EPR, FID-detected EPR, pulse ENDOR, HYSCORE; CW=continuous wave; ENDOR=electron nuclear double resonance; HYSCORE=hyperfine sublevel correlation; FID=free induction decay), and UV-visible spectroscopy. The complexes formed between the parent CuX2 (X=Cl-, Br-, TfO-, SbF6-) salts, the chiral bissulfoximine ligand (S,S)-1, and N-(1-oxoprop-2-en-1-yl)oxazolidin-2-one (2) as the substrate in CH2Cl2 were investigated in frozen and fluid solution. In all cases, penta- or hexacoordinated CuII centers were established. The complexes with counterions indicating high stereoselectivity (TfO- and SbF6-) reveal one unique species in which substrate 2 binds to pseudoequatorial positions (via O atoms), shifting the counterions to axial locations. On the other hand, those lacking stereoselectivity (X=Cl- and Br-) form two species in which the parent halogen anions remain at equatorial positions preventing the formation of geometries compatible with those found for X=TfO- and SbF6-. 相似文献
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Mark Harmer 《Journal of Geometric Analysis》2009,19(2):358-372
We propose geometric conditions equivalent to the discreteness of the spectrum of the Laplacian on a class of Riemannian manifolds
with ends close to warped products. For this class of manifolds we establish a relationship between discreteness of the spectrum
and stochastic incompleteness.
相似文献
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Beattie DA Beaussart A Mierczynska-Vasilev A Harmer SL Thierry B Puskar L Tobin M 《Langmuir : the ACS journal of surfaces and colloids》2012,28(3):1683-1688
Synchrotron FTIR microscopy has been used to probe the structure of model boundary lubricant layers confined at the solid-solid interface. The combination of high brightness of the IR source and a novel contact geometry that uses a hemispherical internal reflection element as the means for light delivery has enabled the detection of <2.5 nm thin monolayer lubricant layers in the solid-solid contact, in addition to allowing for spectral acquisition from specific regions of the contact. Spectra of hydration water from within a confined polyelectrolyte multilayer film have also been acquired, highlighting the altered hydrogen bonding environment within the polymer layer. 相似文献
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L3C3P3: Tricarbontriphosphide Tricyclic Radicals and Cations Stabilized by Cyclic (alkyl)(amino)carbenes
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Dr. Zhongshu Li Yuanfeng Hou Yaqi Li Dr. Alexander Hinz Prof. Dr. Jeffrey R. Harmer Prof. Dr. Cheng‐Yong Su Prof. Dr. Guy Bertrand Prof. Dr. Hansjörg Grützmacher 《Angewandte Chemie (International ed. in English)》2018,57(1):198-202
Alkynes usually oligomerize to give rings with a conjugated π‐electron system. In contrast, phosphaalkynes, R?C≡P, frequently give compounds with polycyclic structures, which are thermodynamically more stable than the corresponding π‐conjugated isomers. The syntheses of the first C3P3 tricyclic compounds are reported with either radical or cationic ground states stabilized by cyclic (alkyl)(amino)carbenes (CAACs). These compounds may be considered as examples of tricarbontriphosphide coordinated by carbenes and are likely formed via trimerization of the corresponding mono‐radicals CAAC‐CP.. The mechanism for the formation of these tricarbontriphosphide radicals has been rationalized by a combination of experiments and DFT calculations. 相似文献
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Dr. Shannon J. Lee Gayatri Viswanathan Dr. Scott L. Carnahan Dr. Colin P. Harmer Dr. Georgiy Akopov Prof. Dr. Aaron J. Rossini Prof. Dr. Gordon J. Miller Prof. Dr. Kirill Kovnir 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(9):e202104319
Centrosymmetric skutterudite RhP3 was converted to a nonsymmorphic and chiral compound RhSi0.3P2.7 (space group P212121) by means of partial replacement of Si for P. The structure, determined by a combination of X-ray crystallography and solid state 31P NMR, exhibits branched polyanionic P/Si chains that are unique among metal phosphides. A driving force to stabilize the locally noncentrosymmetric cis-RhSi2P4 and fac-RhSi3P3 fragments is π-electron back-donation between the Rh t2g-type orbitals and the unoccupied antibonding Si/P orbitals, which is more effective for Si than for P. In situ studies and total energy calculations revealed the metastable nature of RhSi0.3P2.7. Electronic structure calculations predicted centrosymmetric cubic RhP3 to be metallic which was confirmed by transport properties measurements. In contrast, the electronic structure for chiral orthorhombic RhSi0.3P2.7 contained a bandgap, and this compound was shown to be a narrow gap semiconductor. 相似文献