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ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMechanistic Studies on the Hydroxylation of Methane by Methane MonooxygenaseMu-Hyun Baik, Martin Newcomb, Richard A. Friesner, and Stephen J. LippardView Author Information Departments of Chemistry, Columbia University, New York, New York 10027, University of Illinois at Chicago, Chicago, Illinois 60607, and Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 Cite this: Chem. Rev. 2003, 103, 6, 2385–2420Publication Date (Web):May 17,

High-level density functional theory in combination with a continuum solvation model was employed to compute standard redox potentials in solution phase for three different classes of electrochemically active molecules: small organic molecules, metallocenes, and M(bpy) 3 x (M = Fe, Ru, Os; x = +3, +2, +1, 0, −1). Excellent agreement with experimentally determined redox potentials is found with an average deviation of approximately 150 mV when four different solvents commonly in use for electroch

Guiding nitrenes away from a migration Nitrogen conventionally shares its electrons in three bonds with one or more partners. A singly bonded nitrogen, or nitrene, is exceptionally reactive and can insert itself into normally inert C–H bonds. If the nitrene forms next to a carbonyl center, though, it tends to react with the C–C bond on the other side instead. Hong et al. used theory to guide the design of an iridium catalyst that inhibits this rearrangement, steering the nitrene toward C–H inser

The thermodynamics and kinetics for the monofunctional binding of the antitumor drug cisplatin, cis-diamminedichloroplatinum(II), to a purine base site of DNA were studied computationally using guanine and adenine as model reactants. A dominating preference for initial attack at the N7-position of guanine is established experimentally, which is a crucial first step for the formation of a 1,2-intrastrand cross-link of adjacent guanine bases that leads to bending and unwinding of DNA. These struct

Until recently, computational tools were mainly used to explain chemical reactions after experimental results were obtained. With the rapid development of software and hardware technologies to make computational modeling tools more reliable, they can now provide valuable insights and even become predictive. In this review, we highlighted several studies involving computational predictions of unexpected reactivities or providing mechanistic insights for organic and organometallic reactions that l

A novel method for the catalytic asymmetric dearomatization by visible-light-activated [2+2] photocycloaddition with benzofurans and one example of a benzothiophene is reported, thereby providing chiral tricyclic structures with up to four stereocenters including quaternary stereocenters. The benzofurans and the benzothiophene are functionalized at the 2-position with a chelating N-acylpyrazole moiety which permits the coordination of a visible-light-activatable chiral-at-rhodium Lewis acid cata

The development of intermolecular alkene aminopyridylation has great potential for quickly increasing molecular complexity with two valuable groups. Here we report a strategy for the photocatalytic aminopyridylation of alkenes using a variety of N-aminopyridinium salts as both aminating and pyridylating reagents. Using Eosin Y as a photocatalyst, amino and pyridyl groups are simultaneously incorporated into alkenes, affording synthetically useful aminoethyl pyridine derivatives under mild reacti

Quantum chemical molecular modeling has become a standard tool in organometallic chemistry. In particular, density functional theory calculations are now indispensable for investigating the mechanism of even complex reactions and deliver precise energies of intermediates and transition states. Because software packages have become user-friendly and are widely available, even nonexperts can now produce high-quality computer models. In this tutorial, we highlight nontrivial mistakes, misconception

Stereochemical control of electronically excited states is a long-standing challenge in photochemical synthesis, and few catalytic systems that produce high enantioselectivities in triplet-state photoreactions are known. We report herein an exceptionally effective chiral photocatalyst that recruits prochiral quinolones using a series of hydrogen-bonding and π-π interactions. The organization of these substrates within the chiral environment of the transition-metal photosensitizer leads to effici

We report the enantioselective [2+2] cycloaddition of simple cinnamate esters, the products of which are useful synthons for the controlled assembly of cyclobutane natural products. This method utilizes a cocatalytic system in which a chiral Lewis acid accelerates the transfer of triplet energy from an excited-state Ir(III) photocatalyst to the cinnamate ester. Computational evidence indicates that the principal role of the Lewis acid cocatalyst is to lower the absolute energies of the substrate

Despite steady progress in catalytic methods for the borylation of hydrocarbons, methane has not yet been subject to this transformation. Here we report the iridium-catalyzed borylation of methane using bis(pinacolborane) in cyclohexane solvent. Initially, trace amounts of borylated products were detected with phenanthroline-coordinated Ir complexes. A combination of experimental high-pressure and high-throughput screening, and computational mechanism discovery techniques helped to rationalize t

Electrocatalysis is a promising tool for utilizing carbon dioxide as a feedstock in the chemical industry. However, controlling the selectivity for different CO₂ reduction products remains a major challenge. We report a series of manganese carbonyl complexes with elaborated bipyridine or phenanthroline ligands that can reduce CO₂ to either formic acid, if the ligand structure contains strategically positioned tertiary amines, or CO, if the amine groups are absent in the lig

Abstract Metal‐free, visible‐light‐induced site‐selective heteroarylation of remote C(sp 3 )−H bonds has been accomplished through the design of N‐alkoxyheteroarenium salts serving as both alkoxy radical precursors and heteroaryl sources. The transient alkoxy radical can be generated by the single‐electron reduction of an N‐alkoxypyridinium substrate by a photoexcited quinolinone catalyst. Subsequent radical translocation of the alkoxy radical forms a nucleophilic alkyl radical intermediate, whi

The mechanism of the Ir(III)- and Rh(III)-mediated C-N coupling reaction, which is the key step for catalytic C-H amidation, was investigated in an integrated experimental and computational study. Novel amidating agents containing a 1,4,2-dioxazole moiety allowed for designing a stoichiometric version of the catalytic C-N coupling reaction and giving access to reaction intermediates that reveal details about each step of the reaction. Both DFT and kinetic studies strongly point to a mechanism wh