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61.
Activation of Strong Boron–Fluorine and Silicon–Fluorine σ‐Bonds: Theoretical Understanding and Prediction 下载免费PDF全文
Dr. Hajime Kameo Prof. Shigeyoshi Sakaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(39):13588-13597
The oxidative addition of BF3 to a platinum(0) bis(phosphine) complex [Pt(PMe3)2] ( 1 ) was investigated by density functional calculations. Both the cis and trans pathways for the oxidative addition of BF3 to 1 are endergonic (ΔG°=26.8 and 35.7 kcal mol?1, respectively) and require large Gibbs activation energies (ΔG°≠=56.3 and 38.9 kcal mol?1, respectively). A second borane plays crucial roles in accelerating the activation; the trans oxidative addition of BF3 to 1 in the presence of a second BF3 molecule occurs with ΔG°≠ and ΔG° values of 10.1 and ?4.7 kcal mol?1, respectively. ΔG°≠ becomes very small and ΔG° becomes negative. A charge transfer (CT), F→BF3, occurs from the dissociating fluoride to the second non‐coordinated BF3. This CT interaction stabilizes both the transition state and the product. The B?F σ‐bond cleavage of BF2ArF (ArF=3,5‐bis(trifluoromethyl)phenyl) and the B?Cl σ‐bond cleavage of BCl3 by 1 are accelerated by the participation of the second borane. The calculations predict that trans oxidative addition of SiF4 to 1 easily occurs in the presence of a second SiF4 molecule via the formation of a hypervalent Si species. 相似文献
62.
M.Sc. Ayan Dhara Dr. Florian Beuerle 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(48):17391-17396
Boron–nitrogen dative bonds provide a suitable motif for reversible, yet strong and directed interactions, leading to the highly efficient self‐assembly of small organic building blocks into supramolecular cage structures. A bipyramidal [2+3] assembly, as the first example of a supramolecular cage mediated by B?N dative bonds that exists as a discrete species in solution, is quantitatively obtained from a tribenzotriquinacene‐based trisboronate ester and 1,4‐diazabicyclo[2.2.2]octane. Thermodynamic equilibria of cage formation are investigated by isothermal titration calorimetry and fully reversible cage opening can be observed at elevated temperatures. 相似文献
63.
Native Mannose‐Dominant Extraction by Pyridine–Phenol Alternating Oligomers Having an Extremely Efficient Repeating Motif of Hydrogen‐Bonding Acceptors and Donors 下载免费PDF全文
Yuki Ohishi Dr. Hajime Abe Prof. Dr. Masahiko Inouye 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(46):16504-16511
Pyridine–phenol alternating oligomers in which pyridine and phenol moieties are alternatingly linked through acetylene bonds at the 2,6‐positions of the aromatic rings were designed and synthesized. The pyridine nitrogen atom and the neighboring phenolic hydroxyl group were oriented so that they do not form an intramolecular hydrogen bond but cooperatively act as hydrogen‐bonding acceptor and donor in a push–pull fashion for the hydroxyl group of saccharides. The longer oligomer strongly bound to lipophilic glycosides in 1,2‐dichloroethane, and association constants approached 108 M ?1. Moreover, the oligomer extracted native saccharides from a solid phase to apolar organic solvents up to the extent of an equal amount of the oligomer and showed mannose‐dominant extraction among naturally abundant hexoses. The oligomer bound to native saccharides even in 20 % DMSO‐containing 1,2‐dichloroethane and exhibited association constants of greater than 10 M ?1 for D ‐mannose and D ‐glucose. 相似文献
64.
The Cage Structure of IndanCHF3 is Based on the Cooperative Effects of CH⋅⋅⋅π and CH⋅⋅⋅F Weak Hydrogen Bonds 下载免费PDF全文
Dr. Laura B. Favero Weixing Li Lorenzo Spada Dr. Luca Evangelisti Giorgio Visentin Prof. Dr. Walther Caminati 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(45):15970-15973
The structural and energetic features of the C?H???π interaction and the internal dynamics of the CHF3 group change drastically in going from benzene?CHF3 to indan?CHF3, according to the analysis of the rotational spectrum of the latter complex generated in a supersonic expansion. 相似文献
65.
66.
Inside Back Cover: A Reversible Proton Relay Process Mediated by Hydrogen‐Bonding Interactions in [FeFe]Hydrogenase Modeling (Chem. Eur. J. 31/2015) 下载免费PDF全文
67.
Dr. Juan J. Nogueira Dr. Markus Oppel Prof. Leticia González 《Angewandte Chemie (International ed. in English)》2015,54(14):4375-4378
Phenothiazinium dyes are used as photosensitizers in photodynamic therapy. Their mode of action is related to the generation of triplet excited states by intersystem crossing. Therefore, rationalizing the factors that influence intersystem crossing is crucial to improve the efficacy of photodynamic therapy. Here we employ quantum mechanics/molecular mechanics calculations to investigate the effect of aqueous and nucleic acid environments on the intersystem crossing mechanism in methylene blue. We find that the mechanism by which the triplet states are generated depends strongly on the environment. While intersystem crossing in water is mediated exclusively by vibronic spin–orbit coupling, it is enhanced in DNA due to a second pathway driven by electronic spin–orbit coupling. Competing charge‐transfer processes, which are also possible in the presence of DNA, can therefore be suppressed by a suitable structural functionalization, thereby increasing the efficacy of photodynamic therapy. 相似文献
68.
Ana M. Geer Ángel L. Serrano Prof. Bas de Bruin Prof. Miguel A. Ciriano Dr. Cristina Tejel 《Angewandte Chemie (International ed. in English)》2015,54(2):472-475
Complexes with terminal phosphanido (M? PR2) functionalities are believed to be crucial intermediates in new catalytic processes involving the formation of P? P and P? C bonds. We showcase here the isolation and characterization of mononuclear phosphanide rhodium complexes ([RhTp(H)(PR2)L]) that result from the oxidative addition of secondary phosphanes, a reaction that was also explored computationally. These compounds are active catalysts for the dehydrocoupling of PHPh2 to Ph2P? PPh2. The hydrophosphination of dimethyl maleate and the unactivated olefin ethylene is also reported. Reliable evidence for the prominent role of mononuclear phosphanido rhodium species in these reactions is also provided. 相似文献
69.
Dr. Ngong Kodiah Beyeh Dr. Fangfang Pan Acad. Prof. Kari Rissanen 《Angewandte Chemie (International ed. in English)》2015,54(25):7303-7307
Iodine (I2) acts as a bifunctional halogen‐bond donor connecting two macrocyclic molecules of the bowl‐shaped halogen‐bond acceptor, N‐cyclohexyl ammonium resorcinarene chloride 1 , to form the dimeric capsule [(1,4‐dioxane)3@ 1 2(I2)2]. The dimeric capsule is constructed solely through halogen bonds and has a single cavity (V=511 Å3) large enough to encapsulate three 1,4‐dioxane guest molecules. 相似文献
70.
Beyond Molecules: Mesoporous Supramolecular Frameworks Self‐Assembled from Coordination Cages and Inorganic Anions 下载免费PDF全文
Dong Luo Prof. Dr. Xiao‐Ping Zhou Prof. Dr. Dan Li 《Angewandte Chemie (International ed. in English)》2015,54(21):6190-6195
Biological function arises by the assembly of individual biomolecular modules into large aggregations or highly complex architectures. A similar strategy is adopted in supramolecular chemistry to assemble complex and highly ordered structures with advanced functions from simple components. Here we report a series of diamond‐like supramolecular frameworks featuring mesoporous cavities, which are assembled from metal‐imidazolate coordination cages and various anions. Small components (metal ions, amines, aldehydes, and anions) are assembled into the hierarchical complex structures through multiple interactions including covalent bonds, dative bonds, and weak C? H???X (X=O, F, and π) hydrogen bonds. The mesoporous cavities are large enough to trap organic dye molecules, coordination cages, and vitamin B12. The study is expected to inspire new types of crystalline supramolecular framework materials based on coordination motifs and inorganic ions. 相似文献