Cover Feature: Mechanism of Oxidative Activation of Fluorinated Aromatic Compounds by N-Bridged Diiron-Phthalocyanine: What Determines the Reactivity? (Chem. Eur. J. 63/2019)

The biodegradation of compounds with C−F bonds is challenging due to the fact that these bonds are stronger than the C−H bond in methane. In this work, results on the unprecedented reactivity of a biomimetic model complex that contains an N-bridged diiron-phthalocyanine are presented; this model complex is shown to react with perfluorinated arenes under addition of H₂O₂ effectively. To get mechanistic insight into this unusual reactivity, detailed density functional theory calculations on the mechanism of C₆F₆ activation by an iron(IV)-oxo active species of the N-bridged diiron phthalocyanine system were performed. Our studies show that the reaction proceeds through a rate-determining electrophilic C−O addition reaction followed by a 1,2-fluoride shift to give the ketone product, which can further rearrange to the phenol. A thermochemical analysis shows that the weakest C−F bond is the aliphatic C−F bond in the ketone intermediate. The oxidative defluorination of perfluoroaromatics is demonstrated to proceed through a completely different mechanism compared to that of aromatic C−H hydroxylation by iron(IV)-oxo intermediates such as cytochrome P450 Compound I.     

Modular Functionalization of Arenes in a Triply Selective Sequence: Rapid C(sp2) and C(sp3) Coupling of C−Br,C−OTf,and C−Cl Bonds Enabled by a Single Palladium(I) Dimer

Full control over multiple competing coupling sites would enable straightforward access to densely functionalized compound libraries. Historically, the site selection in Pd⁰‐catalyzed functionalizations of poly(pseudo)halogenated arenes has been unpredictable, being dependent on the employed catalyst, the reaction conditions, and the substrate itself. Building on our previous report of C?Br‐selective functionalization in the presence of C?OTf and C?Cl bonds, we herein complete the sequence and demonstrate the first general arylations and alkylations of C?OTf bonds (in <10 min), followed by functionalization of the C?Cl site (in <25 min), at room temperature using the same air‐ and moisture‐stable Pd^I dimer. This allowed the realization of the first general and triply selective sequential C?C coupling (in 2D and 3D space) of C?Br followed by C?OTf and then C?Cl bonds.     

Random walks on stochastic hyperbolic half planar triangulations

We study the simple random walk on stochastic hyperbolic half planar triangulations constructed in (Angel and Ray, Ann Probab, in press). We show that almost surely the walker escapes the boundary of the map in positive speed and that the return probability to the starting point after n steps scales like © 2016 Wiley Periodicals, Inc. Random Struct. Alg., 49, 213–234, 2016     

The Consensus Problem in Polities of Agents with Dissimilar Cognitive Architectures

Agents interacting with their environments, machine or otherwise, arrive at decisions based on their incomplete access to data and their particular cognitive architecture, including data sampling frequency and memory storage limitations. In particular, the same data streams, sampled and stored differently, may cause agents to arrive at different conclusions and to take different actions. This phenomenon has a drastic impact on polities—populations of agents predicated on the sharing of information. We show that, even under ideal conditions, polities consisting of epistemic agents with heterogeneous cognitive architectures might not achieve consensus concerning what conclusions to draw from datastreams. Transfer entropy applied to a toy model of a polity is analyzed to showcase this effect when the dynamics of the environment is known. As an illustration where the dynamics is not known, we examine empirical data streams relevant to climate and show the consensus problem manifest.     

Torsionally broken symmetry assists infrared excitation of biomimetic charge-coupled nuclear motions in the electronic ground state

The concerted interplay between reactive nuclear and electronic motions in molecules actuates chemistry. Here, we demonstrate that out-of-plane torsional deformation and vibrational excitation of stretching motions in the electronic ground state modulate the charge-density distribution in a donor-bridge-acceptor molecule in solution. The vibrationally-induced change, visualised by transient absorption spectroscopy with a mid-infrared pump and a visible probe, is mechanistically resolved by ab initio molecular dynamics simulations. Mapping the potential energy landscape attributes the observed charge-coupled coherent nuclear motions to the population of the initial segment of a double-bond isomerization channel, also seen in biological molecules. Our results illustrate the pivotal role of pre-twisted molecular geometries in enhancing the transfer of vibrational energy to specific molecular modes, prior to thermal redistribution. This motivates the search for synthetic strategies towards achieving potentially new infrared-mediated chemistry.

Channelling vibrational excitation energy to achieve ground-state charge-transfer (CT)-assisted isomerization in a donor-bridge-acceptor molecule in solution.     

Dynamics of networking agents competing for high centrality and low degree

We model a system of networking agents that seek to optimize their centrality in the network while keeping their cost, the number of connections they are participating in, low. Unlike other game-theory based models for network evolution, the success of the agents is related only to their position in the network. The agents use strategies based on local information to improve their chance of success. Both the evolution of strategies and network structure are investigated. We find a dramatic time evolution with cascades of strategy change accompanied by a change in network structure. On average the network self-organizes to a state close to the transition between a fragmented state and a state with a giant component. Furthermore, with increasing system size both the average degree and the level of fragmentation decreases.     

Substituent effect on diastereoselectivity in Type-II ene cyclisation: a theoretical study

Methyl and methoxy substituted transition states (TS) of Type-II ene cyclisation have been optimized by ab-initio method and relative stability of the diastereomeric TSs have been calculated. In all TSs, equatorial substituent positions have been found to be preferred over the axial positions except for the 4′-substituted methoxy derivative, in which the methoxy group prefers to retain axial position. It has also been noted that the presence of the methoxy group(s) in other position(s) may affect the stability of axially oriented TS and thus alters the overall stereoselectivity of the reaction.     

Effect of hetero atom on the conformational stability of the forming ring in the transition structures of Type-II ene cyclization: a theoretical study

The chair conformation of the forming ring in the transition structure, for its high stability, is usually considered for the determination of the overall stereoselectivity in a type-II ene cyclization reaction. However, present theoretical investigation reveals that the presence of a heteroatom like oxygen or nitrogen in the tether of type-II carbonyl ene cyclization stabilizes the transition structure, in which the forming ring adopts a boat conformation. Due to such stability of the boat conformer the overall stereoselectivity of some type-II reactions may differ from the expected one.     

Comparative study on the transition structures of (3,4) and (3,5) ene cyclizations: A theoretical approach

Possible transition structures (TSs) of (3,4) and (3,5) ene cyclizations of 7-methyl-1,6-octadiene and 7-methylocta-1,6-dien-3-one were constructed and optimized by DFT method. Product proportions were calculated using the relative energies of the transition structures and these results are found to be in good agreement with the experimental one. Variation of the product proportions was explained using some model TSs of intermolecular ene reactions. The change of the dihedral angle around the forming carbon–carbon bond in the model transition structures was found to play a crucial role in determining the overall selectivities of cyclized products.