Zhuofeng Ke

Bio: Zhuofeng Ke is an academic researcher from Sun Yat-sen University. The author has contributed to research in topics: Catalysis & Chemistry. The author has an hindex of 32, co-authored 125 publications receiving 3630 citations. Previous affiliations of Zhuofeng Ke include University of North Texas & North Carolina State University.

The ONIOM Method and Its Applications

Abstract: Lung Wa Chung,† W. M. C. Sameera,‡ Romain Ramozzi,‡ Alister J. Page, Miho Hatanaka,‡ Galina P. Petrova, Travis V. Harris,‡,⊥ Xin Li, Zhuofeng Ke, Fengyi Liu, Hai-Bei Li, Lina Ding, and Keiji Morokuma*,‡ †Department of Chemistry, South University of Science and Technology of China, Shenzhen 518055, China ‡Fukui Institute for Fundamental Chemistry, Kyoto University, 34-4 Takano Nishihiraki-cho, Sakyo, Kyoto 606-8103, Japan Newcastle Institute for Energy and Resources, The University of Newcastle, Callaghan 2308, Australia Faculty of Chemistry and Pharmacy, University of Sofia, Bulgaria Boulevard James Bourchier 1, 1164 Sofia, Bulgaria Department of Chemistry, State University of New York at Oswego, Oswego, New York 13126, United States State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, China Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, Shaanxi 710119, China School of Ocean, Shandong University, Weihai 264209, China School of Pharmaceutical Sciences, Zhengzhou University, 100 Kexue Avenue, Zhengzhou, Henan 450001, China

Interfacial Electronic Structure Modulation of NiTe Nanoarrays with NiS Nanodots Facilitates Electrocatalytic Oxygen Evolution.

Abstract: Interface engineering has been recognized as one of the most promising strategies for regulating the physical and chemical properties of materials. However, constructing well-defined nanointerfaces with efficient oxygen evolution reaction (OER) still remains a challenge. Herein, cross columnar NiTe nanoarrays supported on nickel foam are prepared. Subsequently, NiTe/NiS nanointerfaces are constructed by an ion-exchange process. Importantly, the electrocatalytic performance for the OER can be facilitated by coupling NiTe and NiS. As a result, NiTe/NiS shows excellent OER activity with an ultralow overpotential of only 257 mV at a current density of 100 mA cm-2 , and a Tafel slope of 49 mV dec-1 in 1.0 m KOH. The calculated and experimental results reveal that the strong electron interaction on nanointerfaces induces electronic structure modulation, which optimizes the binding energy of *OOH intermediates, thus improving the OER performance.

Homogeneous electrocatalytic water oxidation at neutral pH by a robust macrocyclic nickel(II) complex.

Abstract: The development of an earth-abundant, first-row water oxidation catalyst that operates at neutral pH and low overpotential remains a fundamental chemical challenge. Herein, we report the first nickel-based robust homogeneous water oxidation catalyst, which can electrocatalyze water oxidation at neutral pH and low overpotential in phosphate buffer. The results of DFT calculations verify that the OO bond formation in catalytic water oxidation prefers a HOOH coupling mechanism from a cis-isomer of the catalyst.

Ru(II) catalysts supported by hydridotris(pyrazolyl)borate for the hydroarylation of olefins: reaction scope, mechanistic studies, and guides for the development of improved catalysts.

Abstract: Carbon−carbon bond formation is the central method by which synthetic chemists add complexity, which often represents value, to molecules. Uniting a carbon chain with an aromatic substrate to yield an alkyl arene product is thus a molecular means of creating value-added materials. A traditional method for generating alkyl arenes is Friedel−Crafts catalysis, in which an alkyl halide or olefin is activated to react with an aromatic substrate. Unfortunately, despite the development of new generations of solid-state catalysts, the reaction often requires relatively harsh conditions and frequently gives poor to moderate selectivity. Conversely, a halide can first be incorporated into the aromatic ring, and the aryl halide can subsequently be joined by a variety of catalytic coupling techniques. But generating the aryl halide itself can be problematic, and such methods typically are not atom-economical. The addition of aromatic C−H bonds across the C−C double bonds of olefins (olefin hydroarylation) is therefor...

Carboxylate-assisted transition-metal-catalyzed C-H bond functionalizations: mechanism and scope.

Abstract: The site-selective formation of carbon-carbon bonds through direct functionalizations of otherwise unreactive carbon-hydrogen bonds constitutes an economically attractive strategy for an overall streamlining of sustainable syntheses. In recent decades, intensive research efforts have led to the development of various reaction conditions for challenging C-H bond functionalizations, among which transition-metal-catalyzed transformations arguably constitute thus far the most valuable tool. For instance, the use of inter alia palladium, ruthenium, rhodium, copper, or iron complexes set the stage for chemo-, site-, diastereo-, and/or enantioselective C-H bond functionalizations. Key to success was generally a detailed mechanistic understanding of the elementary C-H bond metalation step, which depending on the nature of the metal fragment can proceed via several distinct reaction pathways. Traditionally, three different modes of action were primarily considered for CH bond metalations, namely, (i) oxidative addition with electronrich late transition metals, (ii) σ-bond metathesis with early transition metals, and (iii) electrophilic activation with electrondeficient late transition metals (Scheme 1). However, more recent mechanistic studies indicated the existence of a continuum of electrophilic, ambiphilic, and nucleophilic interactions. Within this continuum, detailed experimental and computational analysis provided strong evidence for novel C-H bond metalationmechanisms relying on the assistance of a bifunctional ligand bearing an additional Lewis-basic heteroatom, such as that found in (heteroatom-substituted) secondary phosphine oxides or most prominently carboxylates (Scheme 1, iv). This novel insight into the nature of stoichiometric metalations has served as stimulus for the development of novel transformations based on cocatalytic amounts of carboxylates, which significantly broadened the scope of C-H bond functionalizations in recent years, with most remarkable progress being made in palladiumor ruthenium-catalyzed direct arylations and direct alkylations. These carboxylate-assisted C-H bond transformations were mostly proposed to proceed via a mechanism in which metalation takes place via a concerted base-assisted deprotonation. To mechanistically differentiate these intramolecular metalations new acronyms have recently been introduced into the literature, such as CMD (concerted metalationdeprotonation), IES (internal electrophilic substitution), or AMLA (ambiphilic metal ligand activation), which describe related mechanisms and will be used below where appropriate. This review summarizes the development and scope of carboxylates as cocatalysts in transition-metal-catalyzed C-H functionalizations until autumn 2010. Moreover, experimental and computational studies on stoichiometric metalation reactions being of relevance to the mechanism of these catalytic processes are discussed as well. Mechanistically related C-H bond cleavage reactions with ruthenium or iridium complexes bearing monodentate ligands are, however, only covered with respect to their working mode, and transformations with stoichiometric amounts of simple acetate bases are solely included when their mechanism was suggested to proceed by acetate-assisted metalation.

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Abstract: : The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Transition Metal-Catalyzed C–H Amination: Scope, Mechanism, and Applications

Abstract: Catalytic transformation of ubiquitous C–H bonds into valuable C–N bonds offers an efficient synthetic approach to construct N-functionalized molecules. Over the last few decades, transition metal catalysis has been repeatedly proven to be a powerful tool for the direct conversion of cheap hydrocarbons to synthetically versatile amino-containing compounds. This Review comprehensively highlights recent advances in intra- and intermolecular C–H amination reactions utilizing late transition metal-based catalysts. Initial discovery, mechanistic study, and additional applications were categorized on the basis of the mechanistic scaffolds and types of reactions. Reactivity and selectivity of novel systems are discussed in three sections, with each being defined by a proposed working mode.