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Article
Open AccessVoltage-driven control of single-molecule keto-enol equilibrium in a two-terminal junction system
Keto-enol tautomerism, describing an equilibrium involving two tautomers with distinctive structures, provides a promising platform for modulating nanoscale charge transport. However, such equilibria are gener...
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Article
Correction to: The roles of charge transfer and polarization in non-covalent interactions: a perspective from ab initio valence bond methods
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Article
The roles of charge transfer and polarization in non-covalent interactions: a perspective from ab initio valence bond methods
Noncovalent interactions are ubiquitous and have been well recognized in chemistry, biology and material science. Yet, there are still recurring controversies over their natures, due to the wide range of nonco...
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Article
Deciphering the oxygen activation mechanism at the CuC site of particulate methane monooxygenase
The enzymatic oxidation of methane to methanol was discovered in methanotrophs over 110 years ago. Nevertheless, the mechanism of action of particulate methane monooxygenase (pMMO) remains elusive, especially ...
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Article
Open AccessA redox-mediated Kemp eliminase
The acid/base-catalysed Kemp elimination of 5-nitro-benzisoxazole forming 2-cyano-4-nitrophenol has long served as a design platform of enzymes with non-natural reactions, providing new mechanistic insights in...
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Article
Oriented electric fields as future smart reagents in chemistry
No longer a theoretical dream, this Perspective describes effects of oriented external electric fields on rates and selectivity patterns of nonpolar reactions. Discussions of the Diels–Alder reaction, C–H and ...
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New Landscape of Electron-Pair Bonding: Covalent, Ionic, and Charge-Shift Bonds
We discuss here the modern valence bond (VB) description of the electron-pair bond vis-à-vis the Lewis–Pauling model and show that along the two classical families of covalent and ionic bonds, there exists a fami...
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Article
Reply to 'Entropic factors also contribute to the high melting points of polyhedral alkanes'
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Chapter
The V state of ethylene: valence bond theory takes up the challenge
The ground state and first singlet excited state of ethylene, so-called N and V states, respectively, are studied by means of modern valence bond methods. It is found that extremely compact wave functions, made o...
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Article
Identification of a low-spin acylperoxoiron(III) intermediate in bio-inspired non-heme iron-catalysed oxidations
Synthetically useful hydrocarbon oxidations are catalysed by bio-inspired non-heme iron complexes using hydrogen peroxide as oxidant, and carboxylic acid addition enhances their selectivity and catalytic effic...
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Article
The V state of ethylene: valence bond theory takes up the challenge
The ground state and first singlet excited state of ethylene, so-called N and V states, respectively, are studied by means of modern valence bond methods. It is found that extremely compact wave functions, made o...
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Article
Erratum: Exchange-enhanced reactivity in bond activation by metal–oxo enzymes and synthetic reagents
Nature Chemistry 3, 19–27 (2011); published online 15 December 2010; corrected after print 18 April 2012. In the version of this Article originally published, in Fig. 1d the energy levels 4P and 6P were interc...
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Article
Quadruple bonding in C2 and analogous eight-valence electron species
Triple bonding is conventionally considered to be the limit for multiply bonded main group elements, despite higher metal–metal bond orders being frequently observed for transition metals and lanthanides/actin...
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Article
Lessons on O2 and NO bonding to heme from ab initio multireference/multiconfiguration and DFT calculations
This commentary focuses on the conceptual interpretation of the bonding of O2 and NO to heme in oxyheme and nitrosylheme complexes, using high-level ab initio complete active space self-consistent field (CASSCF)/...
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Article
Dihydrogen contacts in alkanes are subtle but not faint
Alkane molecules are held together in the crystal state by purportedly weak homonuclear R–H···H–R dihydrogen interactions. In an apparent contradiction, the high melting points and vaporization enthalpies of p...
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Article
Exchange-enhanced reactivity in bond activation by metal–oxo enzymes and synthetic reagents
Principles based on overlaps and interactions between bonding and antibonding orbitals are known to control chemical reactivity. This Perspective discusses how, for reactions and kinetics of bioinorganic speci...
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Article
Iron opens up to high activity
The iron active sites of enzymes routinely cleave strong C–H bonds, but synthetic complexes have so far been much slower and less efficient. Now, the reactivity of a biomimetic diiron complex has been dramatic...
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Article
Charge-shift bonding and its manifestations in chemistry
The two established models of chemical bonding, covalent and ionic, do not accurately describe all forms of bonds. This article explains how 'charge-shift' bonds — with a large covalent–ionic resonance interac...
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Article
QM/MM theoretical study of the pentacoordinate Mn(III) and resting states of manganese-reconstituted cytochrome P450cam
Quantum mechanical/molecular mechanical (QM/MM) theoretical calculations were performed for the pentacoordinate Mn(III) and water-bound resting states of the Mn-reconstituted mutant of cytochrome P450cam (Mn-P450
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Article
The intrinsic axial ligand effect on propene oxidation by horseradish peroxidase versus cytochrome P450 enzymes
The axial ligand effect on reactivity of heme enzymes is explored by means of density functional theoretical calculations of the oxidation reactions of propene by a model compound I species of horseradish pero...
