We have computed the energies of adsorption of molecular hydrogen on a number of molecular linkers in metal–organic framework solid materials using density functional theory (DFT) and ab initio molecular orbital methods. We fi nd that the hybrid B3LYP (Becke three-parameter Lee–Yang–Parr) DFT method gives a qualitatively incorrect prediction of the hydrogen binding with benzenoid molecular link...

NICS methodology has been applied to study the change in aromaticity in several aromatic rings (benzene, pyrrol, triazine, hexafluorobenzene) on complexation with several ions (Li, Na, K. F, Cl). For this purpose all the isolated and complexed rings have been optimized at the MP2/6-31++G(d,p) level of theory. Using GIAO method to calculate NICS values, the change in aromaticity on complexation ...

Primary cations of the form XCH2CH2 (1) are unstable with respect to the bridged isomer cyclo-(CH2)2X (2) or the hydride-shift isomer CH3CHX (3).Two independent hydrogen isotope experiments for X ) OH demonstrate that gaseous HOCH2CH2 (1a) gives less of its bridged isomer, protonated oxirane (2a), than of its hydride-shift isomer, protonated acetaldehyde (3a).Metastable ion decompositions of io...

Open AccessCCS ChemistryRESEARCH ARTICLE1 Mar 2021New Insights into the Ion-Specific Behaviors and Design Strategies for Ion–π Interactions Zhangyun Liu, Zheng Chen Xin Xu Liu Collaborative Innovation Center of Chemistry Energy Materials, Shanghai Key Laboratory Molecular Catalysis Innovative MOE Computational Physical Sciences, Department Chemistry, Fudan University, 200433 Google Scholar More...

We have recently reported that the binuclear iron complexes Cp*Fe(μ-SR)2(μ,η 2-R2NNH)FeCp* (R = Me, Et; R = Me, Ph; Cp* = ηC5Me5) as novel models of nitrogenase could effectively catalyze the N−N bond cleavage of hydrazines, including NH2NH2 (J. Am. Chem. Soc. 2008, 130, 15250−15251). However, the mechanistic aspects involved in the catalytic cycle and the possibility of reducing N2 by these c...

The effect of light metal (M = Li, Be, Mg, and Al) decoration on the stability of metal organic framework MOF-5 and its hydrogen adsorption is investigated by ab initio and periodic density functional theory (DFT) calculations by employing models of the form BDC:M2:nH2 and MOF-5:M2:nH2, where BDC stands for the benzenedicarboxylate organic linker and MOF5 represents the primitive unit cell. The...

This paper reports computational studies on the ortho alkylation of pyridines via C−H addition to olefins catalyzed by cationic half-sandwich rare-earth alkyl species. A detailed mechanism concerning the generation of catalytically active species and C−H addition has been computationally investigated at the molecular and electronic levels. The results support the mechanism based on experiments,...

Background—Cardiac hypertrophy involves growth responses to a variety of stimuli triggered by increased workload. It is an independent risk factor for heart failure and sudden death. Mammalian target of rapamycin (mTOR) plays a key role in cellular growth responses by integrating growth factor and energy status signals. It is found in 2 structurally and functionally distinct multiprotein comple...