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221.
We report a comprehensive theoretical study on the decarbonylation of acetaldehyde by Fe+ and Cr+. Various intermediates, transition states, and products involved in the decarbonylation reactions are fully optimized at the B3LYP/6-311+G(2df,2pd) level of theory. The potential energy surfaces (PESs) corresponding to [M,O,C2,H4]+(M=Cr and Fe) are examined in detail using B3LYP and CCSD(T) methods, respectively. The validity of these theoretical methods is calibrated with respect to the available thermochemical data. Calculations suggest that the Cr+ mediated decarbonylation of acetaldehyde takes place in four steps on the sextet surface: encounter complexation, C-C activation, aldehyde H-shift, and nonreactive dissociation, in good accordance with the Co+ mediated decarbonylation of acetaldehyde [Zhao, Zhang, Guo, Wu, Lu, Chem. Phys. Lett. 2005, 414, 28], while for the Fe+/acetaldehyde system decarbonylation can occur on both the quartet and the sextet PESs. The quartet pathway, which experiences spin-orbit coupling between the two surfaces, is energetically more favorable; whereas along the sextet decarbonylation coordinate several high-energy barriers are revealed. The theoretical results are compared with the experimental product kinetic energy and angular distributions of decarbonylation of acetaldehyde by Fe+ and Cr+ measured using a crossed-beam technique [Sonnenfroh, Farrar, J. Am. Chem. Soc. 1986, 108, 3521]. 相似文献
222.
Jia Rui Wang Chu Ting Yang Lei Liu Qing Xiang Guo Department of Chemistry University of Science Technology of China Hefei China 《中国化学快报》2007,18(2):133-136
Aerobic oxidation of electron-rich benzylic and phenyl allylic alcohols was achieved with high yields with only 0.1 mol.% of Pd(OAc)2 catalyst in the absence of any ligand. This procedure was expected to be valuable for realistic industrial-scale applications from both economic as well as environmental points of view. 相似文献
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Brena B Zhuang GV Augustsson A Liu G Nordgren J Guo JH Ross PN Luo Y 《The journal of physical chemistry. B》2005,109(16):7907-7914
The electronic structure of pure poly(ethylene oxide) (PEO) for four different polymeric chain conformations has been studied by Hartree-Fock (HF) and density functional theory (DFT) through the analysis of their valence band photoelectron spectroscopy (VB-PES), X-ray emission spectroscopy (XES), and resonant inelastic X-ray scattering (RIXS). It is shown that the valence band of PEO presents specific conformation dependence, which can be used as a fingerprint of the polymeric structures. The calculated spectra have been compared with experimental results for PEO powder. 相似文献
225.
Reaction solutions of selectfluor (1) with triphenylethylene (4a) and tetraphenylethylene (4b) were monitored by ESI-MS and ESI-MS/MS. Detection and characterization of the key radical cationic intermediates 5a.+ and 5b.+) fully supports the SET mechanism in electrophilic fluorination as depicted above. [reaction: see text] 相似文献
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L—半胱氨酸(L—Cys)是蛋白质的降解产物之一,在体内除参与蛋白质的合成外,还参与毒物的解毒过程。本文用pH电位滴定法测定L—Cys同Fe~(2+)、Ni~(2+)、Zn~(2+)、Pb~(2+)形成配合物的稳定常数,以温度系数法获得配位反应的焓变,根据所得的热力学参数,对配位反应的推动力和配合物的结构进行讨论,并进一步用红外光谱和电子光谱对Pb~(2+)、Ni~(2+)两体系所得的结果予以证实。 相似文献