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51.
We report extensive computational studies of some novel intermolecular systems and their properties. Recombination of alkali-halide counterions separated by a noncovalently trapped hydrocarbon molecule is prevented by significant potential energy barriers, resulting in unusual metastable insertion complexes. These systems are extremely polar, while the inserted molecule is strongly counter-polarized, leading to significant cooperative nonadditivity effects. The compression and electric field produced by the counterions favours isomerization of the trapped molecule via a significant reduction of the barriers to bond rearrangement, in a field-induced mechanochemical process. The predicted IR intensity spectra clearly reflect (1) formation of the insertion complex, rather than simple attachment of alkali halide, and (2) isomerization of the trapped molecule, thus allowing experimental access to these events. 相似文献
52.
53.
Data describing the insertion of sulphur dioxide into the carbon―tin bond of a range of substituted phenyltrimethyltin compounds in methanol and benzene solvents have been reconsidered. The reaction in methanol is cleanly second order, but the reaction in benzene has both a second‐order and third‐order component, the latter ascribable to an initial equilibrium formation of a SO2 complex with the phenyl ring followed by the insertion of a second SO2 molecule into the carbon–tin bond. Molecular orbital calculations have identified the transition states (TS) and the favoured reaction pathways for the second‐order and third‐order reaction pathways in benzene. The effects of solvents on TS and enthalpies of reaction have also been examined. New insights into the types of TS involved in electrophilic substitution reactions are revealed. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
54.
《Angewandte Chemie (International ed. in English)》2017,56(40):12064-12084
Magnesium metal is a superior anode which has double the volumetric capacity of lithium metal and has a negative reduction potential of −2.37 V vs. the standard hydrogen electrode. A major benefit of magnesium is the apparent lack of dendrite formation during charging which is one of the crucial concerns of using a lithium metal anode. In this Review, we highlight the foremost research in the development of electrolytes and cathodes and discuss some of the significant challenges which must be overcome in realizing a practical magnesium battery. 相似文献
55.
Joao Marcelo Ribeiro 《Molecular physics》2015,113(13-14):1865-1872
Ab initio and density functional calculations have been performed to elucidate the mechanism of CH radical insertion into methane. The results show that the reaction can be viewed to occur via two stages. On the first stage, the CH radical approaches methane without large structural changes to acquire proper positioning for the subsequent stage, where H-migration occurs from CH4 to CH, along with a C–C bond formation. Where the first stage ends and the second begins, a tight transition state was located using the B3LYP/6-311G(d,p) and MP4(SDQ)/6-311++G(d,p) methods. Using a rigid rotor – harmonic oscillator approach within transition state theory, we show that at the MP5/6-311++G(d,p)//MP4(SDQ)/6-311++G(d,p) level the calculated rate constants are in a reasonably good agreement with experiment in a broad temperature range of 145–581 K. Even at low temperatures, the insertion reaction bottleneck is found about the location of the tight transition state, rather than at long separations between the CH and CH4 reactants. In addition, high level CCSD(T)-F12/CBS calculations of the remainder of the C2H5 potential energy surface predict the CH+CH4 reaction to proceed via the initial insertion step to the ethyl radical which then can emit a hydrogen atom to form highly exothermic C2H4+H products. 相似文献
56.
AbstractA convenient and efficient procedure for the synthesis of 2-substituted-6,7-dihydrobenzo[d]oxazol-4(5H)-ones and 2-aryl-6,7-dihydrobenzofuran-4(5H)-ones through a Rh2(OAc)4-catalyzed C≡X (X?=?N, C) insertion of cyclic 2-diazo-1,3-diketones with nitriles and aromatic alkynes has been developed. This reaction uses readily available starting materials and stable cyclic 2-diazo-1,3-diketone compounds, with desired products formed in good to high yields. A tentative mechanism involving a C≡X bond insertion and 1,5-dipolar electrocyclization/ring opening and cyclization sequence for this reaction is proposed. 相似文献
57.
Dr. David E. Herbert Nadia C. Lara Prof. Theodor Agapie 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(48):16453-16460
The meta‐terphenyl diphosphine, m‐P2, 1 , was utilized to support Ni centers in the oxidation states 0, I, and II. A series of complexes bearing different substituents or ligands at Ni was prepared to investigate the dependence of metal–arene interactions on oxidation state and substitution at the metal center. Complex (m‐P2)Ni ( 2 ) shows strong Ni0–arene interactions involving the central arene ring of the terphenyl ligand both in solution and the solid state. These interactions are significantly less pronounced in Ni0 complexes bearing L‐type ligands ( 2‐L : L=CH3CN, CO, Ph2CN2), NiIX complexes ( 3‐X : X=Cl, BF4, N3, N3B(C6F5)3), and [(m‐P2)NiIICl2] ( 4 ). Complex 2 reacts with substrates, such as diphenyldiazoalkane, sulfur ylides (Ph2S?CH2), organoazides (RN3: R=para‐C6H4OMe, para‐C6H4CF3, 1‐adamantyl), and N2O with the locus of observed reactivity dependent on the nature of the substrate. These reactions led to isolation of an η1‐diphenyldiazoalkane adduct ( 2‐Ph2CN2 ), methylidene insertion into a Ni? P bond followed by rearrangement of a nickel‐bound phosphorus ylide ( 5 ) to a benzylphosphine ( 6) , Staudinger oxidation of the phosphine arms, and metal‐mediated nitrene insertion into an arene C? H bond of 1 , all derived from the same compound ( 2 ). Hydrogen‐atom abstraction from a NiI–amide ( 9 ) and the resulting nitrene transfer supports the viability of Ni–imide intermediates in the reaction of 1 with 1‐azido‐arenes. 相似文献
58.
Carbon‐Coated LiTi2(PO4)3: An Ideal Insertion Host for Lithium‐Ion and Sodium‐Ion Batteries
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Dr. Vanchiappan Aravindan Dr. Wong Chui Ling Steffen Hartung Nicolas Bucher Prof. Srinivasan Madhavi 《化学:亚洲杂志》2014,9(3):878-882
We report the extraordinary performance of carbon‐coated sodium super ion conductor (NASICON)‐type LiTi2(PO4)3 as an ideal host matrix for reversible insertion of both Li and Na ions. The NASICON‐type compound was prepared by means of a Pechini‐type polymerizable complex method and was subsequently carbon coated. Several characterization techniques such as XRD, thermogravimetric analysis (TGA), field‐emission (FE) SEM, TEM, and Raman analysis were used to study the physicochemical properties. Both guest species underwent a two‐phase insertion mechanism during the charge/discharge process that was clearly evidenced from galvanostatic and cyclic voltammetric studies. Unlike that of Li (≈1.5 moles of Li), Na insertion exhibits better reversibility (≈1.59 moles of Na) while experiencing a slightly higher capacity fade (≈8 % higher than Li) and polarization (780 mV) than Li. However, excellent rate capability profiles were noted for Na insertion relative to its counterpart Li. Overall, the Na insertion properties were found to be superior relative to Li insertion, which makes carbon‐coated NASICON‐type LiTi2(PO4)3 hosts attractive for the development of next‐generation batteries. 相似文献
59.
Facile Insertion of Carbon Dioxide into Cu2(μ‐H) Dinuclear Units Supported by Tetraphosphine Ligands
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Kanako Nakamae Dr. Bunsho Kure Prof. Takayuki Nakajima Prof. Yasuyuki Ura Prof. Tomoaki Tanase 《化学:亚洲杂志》2014,9(11):3106-3110
Reactions of meso‐bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm) with CuI species in the presence of NaBH4 afforded di‐ and tetranuclear copper hydride complexes, [Cu2(μ‐H)(μ‐dpmppm)2]X ( 1 ) and [Cu4(μ‐H)2(μ4‐H)(μ‐dpmppm)2]X ( 2 ) (X=BF4, PF6). Complex 1 undergoes facile insertion of CO2 (1 atm) at room temperature, leading to a formate‐bridged dicopper complex [Cu2(μ‐HCOO)(dpmppm)2]X ( 3 ). The experimental and DFT theoretical studies clearly demonstrate that CO2 insertion into the Cu2(μ‐H) unit occurred with the flexible dicopper platform. Complex 2 also undergoes CO2 insertion to give a formate‐bridged complex, [Cu4(μ‐HCOO)3(dpmppm)2]X, during which the square Cu4 framework opened up to a linear tetranuclear chain. 相似文献
60.
Constanze Keck Dr. Jennifer Hahn Divanshu Gupta Prof. Dr. Holger F. Bettinger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(5):e202103614
The boron-nitrogen analogue of ortho-benzyne, 1,2-azaborinine, is a reactive intermediate that features a formal boron-nitrogen triple bond. We here show by combining experimental and computational techniques that the Lewis acidity of the boron center of dibenzo[c,e][1,2]azaborinine allows interaction with the silicon containing single bonds Si−E through the silicon bonding partner E (E=F, Cl, OR, H). The binding to boron activates the Si−E bonds for subsequent insertion reaction. This shows that the BN-aryne is a ferocious species that even can activate and insert into the very strong Si−F bond. 相似文献