排序方式: 共有28条查询结果,搜索用时 15 毫秒
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Han Y Harlan CJ Stoessel P Frost BJ Norton JR Miller S Bridgewater B Xu Q 《Inorganic chemistry》2001,40(13):2942-2952
A series of oxo complexes, Re(O)X(diyne) (X = I, Me, Et), have been prepared from 2,7-nonadiyne and Re(O)I(3)(PPh(3))(2). Addition of B(C(6)F(5))(3) to Re(O)I(2,7-nonadiyne) (5) results in coordination of the oxo ligand to the boron. The protonation of Re(O)(X)(2-butyne)(2) and Re(O)(X)(2,7-nonadiyne)(2) with a variety of acids has been examined. With 5 and HBF(4)/Et(2)O, the ultimate product was [Re(CH(3)CN)(3)(I)(2,7-nonadiyne)](2+) (7). The conversion of 5 to 7 changes the conformation of the diyne ligand from a "chair" to a "boat" and shifts its propargylic protons considerably downfield in the (1)H NMR. The kinetics of the protonation of Re(O)I(2,7-nonadiyne) (5) by CF(3)SO(3)H in CH(3)CN have been monitored by visible spectroscopy, in a stopped-flow apparatus, and by low temperature (1)H NMR. Two second-order rate constants, presumably successive protonations, were observed in the stopped-flow, k(1) = 11.9 M(-)(1) s(-)(1) and k(2) = 3.8 M(-)(1) s(-)(1). Low temperature (1)H NMR spectroscopy indicated that the resulting solution contained a mixture of two doubly protonated intermediates X and Y, each of which slowly formed the product 7 via an acid-independent process. 相似文献
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Sanford TW Allshouse GO Marder BM Nash TJ Mock RC Spielman RB Seamen JF McGurn JS Jobe D Gilliland TL Vargas M Struve KW Stygar WA Douglas MR Matzen MK Hammer JH De Groot JS Eddleman JL Peterson DL Mosher D Whitney KG Thornhill JW Pulsifer PE Apruzese JP Maron Y 《Physical review letters》1996,77(25):5063-5066
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Hualong Song Simon J. Allison Viktor Brabec Hannah E. Bridgewater Jana Kasparkova Hana Kostrhunova Vojtech Novohradsky Roger M. Phillips Jitka Pracharova Nicola J. Rogers Samantha L. Shepherd Peter Scott 《Angewandte Chemie (International ed. in English)》2020,59(34):14677-14685
Monosaccharides are added to the hydrophilic face of a self‐assembled asymmetric FeII metallohelix, using CuAAC chemistry. The sixteen resulting architectures are water‐stable and optically pure, and exhibit improved antiproliferative selectivity against colon cancer cells (HCT116 p53+/+) with respect to the non‐cancerous ARPE‐19 cell line. While the most selective compound is a glucose‐appended enantiomer, its cellular entry is not mainly glucose transporter‐mediated. Glucose conjugation nevertheless increases nuclear delivery ca 2.5‐fold, and a non‐destructive interaction with DNA is indicated. Addition of the glucose units affects the binding orientation of the metallohelix to naked DNA, but does not substantially alter the overall affinity. In a mouse model, the glucose conjugated compound was far better tolerated, and tumour growth delays for the parent compound (2.6 d) were improved to 4.3 d; performance as good as cisplatin but with the advantage of no weight loss in the subjects. 相似文献
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Schoonover JR Dattelbaum DM Osborn JC Bridgewater JS Kenney JW 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2003,59(2):309-319
The effects of hydrostatic pressure upon (1) a segmented poly (ester urethane), (2) a hydrolytically degraded sample of the same polymer, and (3) models for the polyurethane and polyester segments in this polymer have been studied by Fourier transform infrared spectroscopy using high-pressure diamond anvil cells (DACs). The pressure responses of the vibrational frequencies of specific functional groups of the poly (ester urethane) in the 0-100-kbar range are compared with data for individual segment models and the partially degraded sample. The results indicated that the polymer is highly stable in this pressure regime, with no measurable degradation or phase changes. Differences in the pressure dependency of specific infrared bands between the poly (ester urethane) sample and the partially degraded sample are slight and consistent with changes in hydrogen-bonding interactions and shorter chain lengths in the degraded sample. 相似文献
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Chung SH Gokirmak A Wu DH Bridgewater JS Ott E Antonsen TM Anlage SM 《Physical review letters》2000,85(12):2482-2485
We present experimental results on eigenfunctions of a wave chaotic system in the continuous crossover regime between time-reversal symmetric and time-reversal symmetry-broken states. The statistical properties of the eigenfunctions of a two-dimensional microwave resonator are analyzed as a function of an experimentally determined time-reversal symmetry-breaking parameter. We test four theories of one-point eigenfunction statistics and introduce a new theory relating the one-point and two-point statistical properties in the crossover regime. We also find a universal correlation between the one-point and two-point statistical parameters for the crossover eigenfunctions. 相似文献
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An integral equation formulation for buoyancy-driven convection problems is developed and illustrated. Buoyancy-driven convection in a bounded cylindrical geometry with a free surface is studied for a range of aspect ratios and Nusselt numbers. The critical Rayleigh number, the nature of the cellular motion, and the heat transfer enhancement are computed using linear theory. Green's functions are used to convert the linear problem into linear Fredholm integral equations. Theorems are proved which establish the properties of the eigenvalues and eigenfunctions of the linear integral operator which appears in these equations. 相似文献
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Abstract— This article provides a brief overview of time-resolved infrared spectroscopy (TRIR) applied to the investigation of organometallic photochemistry in solution. In this context, some fundamental problems where flash photolysis TRIR techniques may provide information relevant to photochemical pathways and to certain thermal reaction mechanisms are described. Different approaches to obtaining TRIR spectral information are summarized and illustrated with specific applications. 相似文献
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Andrei S. Batsanov Brian M. Bridgewater Judith A. K. Howard Andrew K. Hughes Claire Wilson 《Journal of organometallic chemistry》1999,590(2):1657-179
Reaction of phenyl magnesium bromide with the ,β-unsaturated ketone 3-methyl-2,3,4,5,6,7-hexahydroind-8(9)-en-1-one, followed by an aqueous work-up, generates the pro-chiral tetra-substituted cyclopentadiene, 1-phenyl-3-methyl-4,5,6,7-tetrahydroindene, Cp‡H, a precursor to the η5-cyclopentadienyl ligand in (Cp‡)2Fe and [(Cp‡)Fe(CO)]2(μ-CO)2. Both complexes were generated as mixtures of rac-(RR and SS)- and meso-(RS)-isomers, and in either case pure meso-isomer was isolated by crystallisation and characterised by single crystal X-ray structure, both molecules having crystallographic Ci symmetry. Reduction with Na/Hg cleaves meso-(RS)-[(Cp‡)Fe(CO)]2(μ-CO)2 and the resulting mixture of (R)- and (S)-[(Cp‡)Fe(CO)2]− anions reacts with MeI to give racemic (Cp‡)Fe(CO)2Me, which was characterised by the X-ray crystal structure. The Cp‡ ligand is more electron donating than (η-C5H5) as revealed by the reduction potential of the (Cp‡)2Fe+/(Cp‡)2Fe couple, E°=−0.127 V (vs. Ag AgCl). Reaction of LiCp‡ with ZrCl4 yields the zirconocene dichloride [Zr(Cp‡)2Cl2] as mixture of rac- and meso-isomers, from which pure rac-isomer is obtained as a mixture of RR and SS crystals by recrystallisation. The reaction of rac-[Zr(Cp‡)2Cl2] with LiMe gives rac-[Zr(Cp‡)2Me2]. The structures of RR-[Zr(Cp‡)2Cl2] and rac-[Zr(Cp‡)2Me2] have been determined by X-ray diffraction. The structural studies reveal the influence of the bulky substituted cyclopentadienyl ligand on the metal---Cp‡ distances and other metric parameters. 相似文献