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排序方式: 共有125条查询结果,搜索用时 31 毫秒
1.
David S. McGuinness Edward L. Marshall Vernon C. Gibson Jonathan W. Steed 《Journal of polymer science. Part A, Polymer chemistry》2003,41(23):3798-3803
Hetero‐bimetallic Fe(II) alkoxide/aryloxides were evaluated as initiators for the ring‐opening polymerization of rac‐lactide. [(THF)NaFe(OtBu)3]2 ( 1 ) and [(THF)4Na2Fe(2,6‐diisopropylphenolate)4] ( 2 ) (THF = tetrahydrofuran) both polymerized lactide efficiently at room temperature, with complex 1 affording better control over the molecular weight parameters of the resultant polymer. At conversions below 70%, a linear increase in molecular weight with conversion was observed, indicative of a well‐controlled polymerization process. Complex 2 is the first example of a dianionic Fe(II) alkoxide and has been structurally characterized to reveal a distorted square planar FeO4 array in which both Na counterions bridge two aryloxide ligands and are further complexed by two THF ligands. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3798–3803, 2003 相似文献
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Oxyallyl cations generated in situ from dihaloketones have been found to undergo the Favorskii rearrangement in preference to an intramolecular Type-II 4 + 3 cycloaddition reaction in trifluoroethanol and hexafluoropropan-2-ol solvents, generating acrylate esters with high cis selectivity. A synthetic alternative to the intramolecular Type-II 4 + 3 cycloaddition has been developed on the basis of intramolecular enolate alkylation to close a 7-membered ring with an exocyclic double bond. 相似文献
4.
Hogarth G Holman KT Pateman A Sella A Steed JW Richards I 《Dalton transactions (Cambridge, England : 2003)》2005,(16):2688-2695
The iodine(III) reagent, PhI[double bond, length as m-dash]NTs, acts as a source of the nitrene fragment NTs, which undergoes facile insertion into the metal-sulfur bonds of a range of dithiocarbamate complexes. Addition of two equivalents of PhI=NTs to [M(S(2)CNR2)2] affords sulfido-amido complexes [M{SC(NR2)SNTs}2](M=Ni, Cu), which insert two further nitrene fragments to afford zwitterionic tetraamido complexes [M{TsNSC(NR2)SNTs}2](M=Co, Ni, Cu). Crystallographic studies have been carried out on both types of complex allowing possible resonance hydrids of the new ligand types to be assessed. 相似文献
5.
Gibson SE Kaufmann KA Loch JA Steed JW White AJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(8):2566-2576
Understanding the interaction of chiral ligands, alkynes, and alkenes with cobaltcarbonyl sources is critical to learning more about the mechanism of the catalytic, asymmetric Pauson-Khand reaction. We have successfully characterized complexes of the type [Co2(alkyne)(binap)(CO)4] (BINAP=(1,1'-binaphthalene)-2,2'-diylbis(diphenylphosphine)) and shown that diastereomer interconversion occurs under Pauson-Khand reaction conditions when alkyne=HC[triple bond]CCO2Me. Attempts to isolate [Co2(alkyne)(binap)(CO)x] complexes with coordinated alkenes led to the formation of cobaltacyclopentadiene species. 相似文献
6.
A two-dimensional (2-D) model of the atmosphere including photochemistry as complete as that in advanced 1-D models, parameterized transport, diurnal effects and rayleigh scattering has been used to calculate present day altitude profiles of trace species mixing ratios.The structure and content of the model will be described and a comparison of model results with atmospheric measurements will be presented.In particular, while there had been some expectation that inclusion of latitudinal and seasonal effects would resolve certain major discrepancies for atmospheric chlorine species, the current profiles for 30 degrees latitude are qualitatively similar to 1-D model results and seasonal variations are relatively small. The principle discrepancies between 1-D model results and measurements including overstimation by the model of ClO concentrations below 30 km and understimation of HCl above 30 km are still present in the 2-D model results.The absence of change in HCl also imploies that over-estimation of HF/HCl ratio above 20 km remains a problem.The implications for model validation and ozone depletion calculations, in the view of the effect of chlorofluorocarbons, will be discussed. 相似文献
7.
Zinc(II) and tin(II) derivatives of maltol (Hmalt), ethylmaltol (HEtmalt), tropolone (Htrop), hinokitiol (Hhino), and kojic acid (Hkoj) have been prepared and characterized, and the crystal structures of M(trop)(2) (M = Zn, Sn), Zn(hino)(2).EtOH, and Sn(malt)(2) have been determined. The Zn(trop)(2) is a polymeric structure in which tropolone has both a bridging and chelating role; zinc(hino)(2) crystallizes as an ethanol adduct of which the structure is a dimeric fragment of the Zn(trop)(2) polymer and in which each metal is "capped" by a molecule of alcohol. The tin complexes are notably air-stable despite adopting monomeric pseudo-trigonal-bipyramidal structures (SnO(4)E; E is a stereochemically active lone electron pair) in which the ligands only chelate a single metal center. 相似文献
8.
Turner DR Henry M Wilkinson C McIntyre GJ Mason SA Goeta AE Steed JW 《Journal of the American Chemical Society》2005,127(31):11063-11074
Four isomorphous complexes of formula [M(L)(4)(H(2)O)(2)]SO(4).2H(2)O (M = Co, 1a; Ni, 1b; Cu, 1c; Zn, 1d) have been isolated and characterized by single-crystal X-ray diffraction and neutron diffraction using the quasi-Laue diffractometer VIVALDI at the Institut Laue-Langevin as well as by thermogravimetric analysis. The structures contain a discrete, strongly hydrogen-bonded water tetramer which causes a significant distortion of the metal coordination sphere in each case. Partial atomic charges and hardness analysis (PACHA) calculations reveal that the shortest hydrogen bonds are not the strongest in this constrained, cyclic solid-state structure and show that the distortion at the metal center is caused by the drive to maintain the integrity of the water tetramer. The system undergoes a disorder-order transition on slow cooling that provides insight into the nature of communication between water squares. 相似文献
9.
Six X-ray crystal structures are reported, all containing substituted triphenylmethanol derivative 4 either alone or as its mono or bis(chromium tricarbonyl) complexes. All four chromium complexes studied crystallize with two independent molecules in the crystallographic asymmetric unit. It is demonstrated that from the X-ray crystal structure of the acentric racemic (+/-)-(1pR,1' 'R)(1pS,1' 'S)-[Cr(CO)(3)(eta(6)-t-BuC(6)H(3)(CMeOMe)CPh(2)OH)], (+/-)-3, it is possible to deduce the 4-fold helical structure of the chiral (-)-(1pR,1' 'R) isomer, (-)-3. The bimetallic derivatives demonstrate the ability to control intermolecular interactions by the positioning of relative stereochemistry. 相似文献
10.
Prof. Dr. Mateo Alajarin Dr. Raul‐Angel Orenes Prof. Dr. Judith A. K. Howard Dr. Elinor C. Spencer Prof. Dr. Jonathan W. Steed Dr. Aurelia Pastor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(8):2389-2397
Tris(2‐ and 3‐ureidobenzyl)amines with Cs symmetry self‐assemble in solution forming mixtures of regioisomeric capsular aggregates, one of which is chiral and the other centrosymmetric. Under certain conditions, a predominance of the centrosymmetric regioisomer is found before equilibrium, that is, a mixture close to the statistical ratio of the two species is reached. In the solid state, there is a preference for the centrosymmetric capsules. Molecular models of both regioisomeric aggregates have been built and analyzed for comparison. Guests inside capsules formed by self‐assembly of desymmetrized tris(3‐ureidobenzyl)amines feel different magnetic environments, depending on whether they are inside a chiral or an achiral regioisomeric container. Of special significance are the experiments with a more flexible triurea endowed with an ureidopropylic arm, which self‐assembles with the same efficiency as the more rigid tris(ureidobenzyl)amines. 相似文献