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991.
Redox‐Active Tetraruthenium Macrocycles Built from 1,4‐Divinylphenylene‐Bridged Diruthenium Complexes 下载免费PDF全文
Stefan Scheerer Dr. Michael Linseis Dr. Evelyn Wuttke Sabrina Weickert Prof. Dr. Malte Drescher Dr. Oliver Tröppner Prof. Dr. Ivana Ivanović‐Burmazović Andreas Irmler Prof. Dr. Fabian Pauly Prof. Dr. Rainer F. Winter 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9574-9590
Metallamacrocylic tetraruthenium complexes were generated by treatment of 1,4‐divinylphenylene‐bridged diruthenium complexes with functionalized 1,3‐benzene dicarboxylic acids and characterized by HR ESI‐MS and multinuclear NMR spectroscopy. Every divinylphenylene diruthenium subunit is oxidized in two consecutive one‐electron steps with half‐wave potential splittings in the range of 250 to 330 mV. Additional, smaller redox‐splittings between the +/2+ and 0/+ and the 3+/4+ and 2+/3+ redox processes, corresponding to the first and the second oxidations of every divinylphenylene diruthenium entity, are due to electrostatic effects. The lack of electronic coupling through bond or through space is explained by the nodal properties of the relevant molecular orbitals and the lateral side‐by‐side arrangement of the divinylphenylene linkers. The polyelectrochromic behavior of the divinylphenylene diruthenium precursors is retained and even amplified in these metallamacrocyclic structures. EPR studies down to T=4 K indicate that the dications 1‐H2+ and 1‐OBu2+ are paramagnetic. The dications and the tetracation of macrocycle 3‐H display intense (dications) or weak ( 3‐H4+ ) EPR signals. Quantum chemical calculations indicate that the four most stable conformers of the macrocycles are largely devoid of strain. Bond parameters, energies as well as charge and spin density distributions of model macrocycle 5‐HMe were calculated for the different charge and spin states. 相似文献
992.
通过对河道一级阶地粗砂层局部软弱地基进行换填处理的工程实例的分析,总结了换填处理对该地层的经济实用性,拓宽了换填处理及天然地基的应用范围,克服了该类场地桩基施工的难点,节省了工期和造价.同时积累了级配砂石换填处理的施工经验. 相似文献
993.
《International journal of quantum chemistry》2018,118(16)
CCSD(T)/CBS and DFT methods are employed to study the stacking interactions of acetylacetonate‐type (acac‐type) chelates of nickel, palladium, and platinum with benzene. The strongest chelate–aryl stacking interactions are formed by nickel and palladium chelate, with interaction energies of −5.75 kcal mol−1 and −5.73 kcal mol−1, while the interaction of platinum chelate is weaker, with interaction energy of −5.36 kcal mol−1. These interaction energies are significantly stronger than stacking of two benzenes, −2.73 kcal mol−1. The strongest nickel and palladium chelate–aryl interactions are with benzene center above the metal area, while the strongest platinum chelate–aryl interaction is with the benzene center above the C2 atom of the acac‐type chelate ring. These preferences arise from very different electrostatic potentials above the metal ions, ranging from very positive above nickel to slightly negative above platinum. While the differences in electrostatic potentials above metal atoms cause different geometries with the most stable interaction among the three metals, the dispersion (correlation energy) component is the largest contribution to the total interaction energy for all three metals. 相似文献
994.
Exploring the Reactivity of α‐Lithiated Aryl Benzyl Ethers: Inhibition of the [1,2]‐Wittig Rearrangement and the Mechanistic Proposal Revisited 下载免费PDF全文
Rocío Velasco Dr. Carlos Silva López Dr. Olalla Nieto Faza Prof. Dr. Roberto Sanz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(42):15058-15068
By carefully controlling the reaction temperature, treatment of aryl benzyl ethers with tBuLi selectively leads to α‐lithiation, generating stable organolithiums that can be directly trapped with a variety of selected electrophiles, before they can undergo the expected [1,2]‐Wittig rearrangement. This rearrangement has been deeply studied, both experimentally and computationally, with aryl α‐lithiated benzyl ethers bearing different substituents at the aryl ring. The obtained results support the competence of a concerted anionic intramolecular addition/elimination sequence and a radical dissociation/recombination sequence for explaining the tendency of migration for aryl groups. The more favored rearrangements are found for substrates with electron‐poor aryl groups that favor the anionic pathway. 相似文献
995.
Electrochemical oxidation of 2,3‐dihydroxypyridine in aqueous phosphate buffer solution at a glassy carbon electrode has been studied using cyclic voltammetry and controlled potential coulometry. The results indicate that oxidation of 2,3‐dihydroxypyridine on glassy carbon electrode shows an irreversible feature in aqueous solution. This data indicates that the electrochemically generated pyridindione is unstable and via an oxidative conversion pathway converts to a novel highly oxygenated heterocyclic compound. By means of the obtained electrochemical data, an efficient, one‐pot method for the synthesis of this heterocyclic compound based on the oxidative cyclization of 2,3‐dihydroxypyridine under green conditions, and in a good yield and purity is described. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
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M. Sc. Florian Hofbauer Prof. Dr. Irmgard Frank 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(51):16332-16338
Previous single‐molecule atomic force microscopy (AFM) experiments showed a change in the reactivity of a bimolecular substitution reaction with a definite force acting on a protein containing disulfide bonds. Using Car–Parrinello molecular dynamics (CPMD) simulations, we analyse the relevant reaction pathways for the breaking of a disulfide bond in the presence of nucleophiles. 相似文献