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61.
A kinetic study of Diels-Alder additions between norbornene derivatives acting as dienophiles and the dienes tropone, perchlorocyclopentadiene and 9,10-dimethylanthracene is presented. The results suggest that tropone thereby acts as an electron acceptor, classifying these reactions then as Diels-Alder additions with ‘inverse electron demand’. The role of non-reacting double bonds was investigated using 7-alkylidenorbornene derivatives as dienophiles. These show comparable reactivity in ‘normal’ but enhanced reactivity in ‘inverse electron demand’ Diels-Alder additions. This outcome is interpreted in terms of frontier orbital interactions between the reactants using photoelectron spectroscopical results as a basis for the qualitative perturbation treatment. It is suggested that the enhanced reactivity in the case of the 7-alkylidene derivatives does not necessitate the consideration of a direct (‘through-space’) participation of the non-reacting double bond. 相似文献
62.
63.
Bockstaller MR Lapetnikov Y Margel S Thomas EL 《Journal of the American Chemical Society》2003,125(18):5276-5277
Dependent on the relative particle core size, two distinct types of particle topologies in block copolymer/nanocrystal blends have been identified, that is, the localization of particles along the intermaterial dividing surface or at the center of the respective polymer domain. In ternary systems consisting of block copolymer and two different-sized nanocrystal species, the distinct morphological types are conserved, resulting in autonomous size-selective separation and organization of the respective nanocrystals within alternating arrays and sheets. 相似文献
64.
Elettra L. Piacentino Edwin Rodriguez Kevin Parker Thomas M. Gilbert Richard A. J. O'Hair Victor Ryzhov 《Journal of mass spectrometry : JMS》2019,54(6):520-526
Gas‐phase C―C coupling reactions mediated by Ni (II) complexes were studied using a linear quadrupole ion trap mass spectrometer. Ternary nickel cationic carboxylate complexes, [(phen)Ni (OOCR1)]+ (where phen = 1,10‐phenanthroline), were formed by electrospray ionization. Upon collision‐induced dissociation (CID), they extrude CO2 forming the organometallic cation [(phen)Ni(R1)]+, which undergoes gas‐phase ion‐molecule reactions (IMR) with acetate esters CH3COOR2 to yield the acetate complex [(phen)Ni (OOCCH3)]+ and a C―C coupling product R1‐R2. These Ni(II)/phenanthroline‐mediated coupling reactions can be performed with a variety of carbon substituents R1 and R2 (sp3, sp2, or aromatic), some of them functionalized. Reaction rates do not seem to be strongly dependent on the nature of the substituents, as sp3‐sp3 or sp2‐sp2 coupling reactions proceed rapidly. Experimental results are supported by density functional theory calculations, which provide insights into the energetics associated with the C―C bond coupling step. 相似文献
65.
Preparation and Characterization of α,ω-Dihydroperchloro Silanes Synthesis for the new compounds H(SiCl2)nH, n = 3?7 and HSi4Cl5 were described, starting from the perphenylated cyclosilanes. The new compounds were characterized and 1H- and 29Si-NMR spectra are discussed. 相似文献
66.
Humphry T Forconi M Williams NH Hengge AC 《Journal of the American Chemical Society》2002,124(50):14860-14861
Isotope effects in the nucleophile and in the leaving group were measured to gain information about the mechanism and transition state of the hydrolysis of methyl p-nitrophenyl phosphate complexed to a dinuclear cobalt complex. The complexed diester undergoes hydrolysis about 1011 times faster than the corresponding uncomplexed diester. The kinetic isotope effects indicate that this rate acceleration is accompanied by a change in mechanism. A large inverse 18O isotope effect in the bridging hydroxide nucleophile (0.937 +/- 0.002) suggests that nucleophilic attack occurs before the rate-determining step. Large isotope effects in the nitrophenyl leaving group (18Olg = 1.029 +/- 0.002, 15N = 1.0026 +/- 0.0002) indicate significant fission of the P-O ester bond in the transition state of the rate-determining step. The data indicate that in contrast to uncomplexed diesters, which undergo hydrolysis by a concerted mechanism, the reaction of the complexed diester likely proceeds via an addition-elimination mechanism. The rate-limiting step is expulsion of the p-nitrophenyl leaving group from the intermediate, which proceeds by a late transition state with extensive bond fission to the leaving group. This represents a substantial change in mechanism from the hydrolysis of uncomplexed aryl phosphate diesters. 相似文献
67.
The dynamic processes of N(1s) core-hole excitation in gas-phase CH3CN molecule have been studied at both Hartree-Fock and hybrid density-functional theory levels. The vibrational structure is analyzed for fully optimized core-excited states. Frank-Condon factors are obtained using the linear coupling model for various potential surfaces. It is found that the vibrational profile of the N-K absorption can be largely described by a summation of two vibrational progressions: a structure-rich profile of nu(CN) stretching mode and a large envelope of congestioned vibrational levels related to the strong (-C-CN) terminal bending bond. Excellent agreement between theoretical and experimental spectra is obtained. 相似文献
68.
Computer least-squares methods are used to conduct an automatic reverse search of a library of complete mass spectra for the analysis of the output data matrix from a g.c.—m.s. system. The search is limited to those mass spectra falling within a narrow retention index window about the retention index corresponding to each scan in the datamatrix. The least-squares estimated parameters obtained are proportional to the concentrations of the substances present at each scan and are displayed graphically as the profiles of resolved overlapping g.c. peaks. The precision of the parameters is estimated. The root mean square Values of the residuals of the least-squares fits are used successfully to indicate the presence of substances not in the library. Examples are given of the results produced with data from this laboratory. Possible elaborations and improvements of this computer program are discussed. 相似文献
69.
70.
Li Pang Edwin A. C. Lucken Gérald Bernardinelli 《Journal of inclusion phenomena and macrocyclic chemistry》1992,13(1):63-76
NQR spectroscopy and X-ray crystallography have been jointly applied to the study of the small guest molecules CH2Cl2, CHCl3, CCl4, CBr2Cl2, C(CH3)2Cl2 etc. in the Werner host complex Ni(SCN)2(3-methylpyridine)4. Specific host-guest dipole-dipole interactions play an important role in order-disorder effects for guest molecules in the cavities of orthorhombic system,Fddd. Thus a weakly polar molecule such as CBr2Cl2 exhibits a disordered alternation, both the bromine and the chlorine atoms occupying the two possible sites in theC
2 cavity, whereas for the polar molecule C(CH3)2Cl2, an ordered structure is observed. In addition, two new types of crystal structures,C2/c andP
, are reported here for dichloromethane and chloroform clathrates. 相似文献