Volume 2 Issue 2, February 2019

Volume 2 Issue 2

Shifting reactivity pathways

Due to electronic effects, certain activating groups in organic molecules can increase the reactivity of nearby bonds. Now, Lichosyt et al. have shown that such activating groups can be transiently introduced into otherwise unreactive molecules by catalytic reversible reactions. When combined with subsequent catalytic functionalization reactions, the constructed networks of reactions enable the simple functionalization of normally unreactive sites.

See Lichosyt et al.

Image: Adrian Grosu (stock.adobe.com) and Paweł Dydio (University of Strasbourg). Cover Design: Karen Moore.

Editorial

  • Editorial |

    Preprints are openly available non-peer-reviewed manuscripts that precede the actual peer-reviewed publication. We analyse this phenomenon that is gaining popularity across all areas of catalysis.

Comment & Opinion

Research Highlights

Reviews

  • Perspective |

    Desalination processes generally leave brine as a by-product, which is then discharged back into the environment. This Perspective looks at recent procedures for using this brine instead as resource for the production of hydrochloric acid and sodium hydroxide through direct electrosynthesis.

    • Amit Kumar
    • , Katherine R. Phillips
    • , Gregory P. Thiel
    • , Uwe Schröder
    •  & John H. Lienhard V

Research

  • Article |

    The ability to functionalize normally unreactive sites in molecules opens up tremendous flexibility in synthesis design and structural modification, in addition to reducing the need for multiple steps or highly reactive reagents. Now, a dual-catalytic strategy, demonstrated with the methods for the β-arylation of aliphatic alcohols and for the enantioselective γ-hydroarylation of allylic alcohols, is reported for such reactions.

    • Dawid Lichosyt
    • , Yang Zhang
    • , Karolina Hurej
    •  & Paweł Dydio
  • Article |

    Despite the many recent developments in iron-catalysed cross-couplings, the mechanistic understanding of these reactions is lacking compared to the more studied palladium and nickel variants. Here, the authors find that during iron-catalysed Negishi reactions the diphosphine ligand predominately binds to the zinc—rather than the iron—centre.

    • Antonis M. Messinis
    • , Stephen L. J. Luckham
    • , Peter P. Wells
    • , Diego Gianolio
    • , Emma K. Gibson
    • , Harry M. O’Brien
    • , Hazel A. Sparkes
    • , Sean A. Davis
    • , June Callison
    • , David Elorriaga
    • , Oscar Hernandez-Fajardo
    •  & Robin B. Bedford
  • Article |

    Carbon-based single-atom catalysts usually rely on nitrogen co-doping to stabilize the single metal atoms as metal–N4 moieties. Now, Wei, Yao and colleagues make use of operando techniques to show that under alkaline hydrogen evolution reaction conditions the Co–N4 active site undergoes structural distortion to a HO–Co–N2 configuration.

    • Linlin Cao
    • , Qiquan Luo
    • , Wei Liu
    • , Yue Lin
    • , Xiaokang Liu
    • , Yuanjie Cao
    • , Wei Zhang
    • , Yuen Wu
    • , Jinlong Yang
    • , Tao Yao
    •  & Shiqiang Wei
  • Article |

    MOFs have found limited application in catalysis so far, as the result of their limited thermal and hydrolytic stability. Now, non-thermal plasma is shown to be able to promote and sustain the activity of HKUST-1 and other MOFs towards the water–gas shift reaction despite the presence of water.

    • Shaojun Xu
    • , Sarayute Chansai
    • , Cristina Stere
    • , Burapat Inceesungvorn
    • , Alexandre Goguet
    • , Kanlayawat Wangkawong
    • , S. F. Rebecca Taylor
    • , Nadeen Al-Janabi
    • , Christopher Hardacre
    • , Philip A. Martin
    •  & Xiaolei Fan
  • Article |

    Single-atom catalysts are receiving much attention, but insights into their active sites or the differences in reactivity with conventional nanoparticles are still controversial. Now, operando studies on CO oxidation with Ir/MgAl2O4 accompanied by computational investigations reveal important features of this class of catalyst.

    • Yubing Lu
    • , Jiamin Wang
    • , Liang Yu
    • , Libor Kovarik
    • , Xiwen Zhang
    • , Adam S. Hoffman
    • , Alessandro Gallo
    • , Simon R. Bare
    • , Dimosthenis Sokaras
    • , Thomas Kroll
    • , Vanessa Dagle
    • , Hongliang Xin
    •  & Ayman M. Karim
  • Article |

    The selective catalytic oxidation of ammonia with palladium is an important reaction in the context of NOx abatement, although limited structural information about the catalyst under reaction conditions is available. Now, an operando study reveals the speciation of palladium and identifies crucial palladium–nitride species.

    • Ellie K. Dann
    • , Emma K. Gibson
    • , Rachel H. Blackmore
    • , C. Richard A. Catlow
    • , Paul Collier
    • , Arunabhiram Chutia
    • , Tugce Eralp Erden
    • , Christopher Hardacre
    • , Anna Kroner
    • , Maarten Nachtegaal
    • , Agnes Raj
    • , Scott M. Rogers
    • , S. F. Rebecca Taylor
    • , Paul Thompson
    • , George F. Tierney
    • , Constantinos D. Zeinalipour-Yazdi
    • , Alexandre Goguet
    •  & Peter P. Wells
  • Article |

    Hydrogen atom transfer processes are commonly encountered in chemical and biological systems. Here the authors report a redox-neutral hydrogen atom transfer through the activation of hydrosilanes with a Lewis base. Further, they demonstrate that this initial step can be directed towards hydrosilylation or polymerization depending on the choice of catalyst.

    • Parham Asgari
    • , Yuanda Hua
    • , Apparao Bokka
    • , Chanachon Thiamsiri
    • , Watcharapon Prasitwatcharakorn
    • , Ashif Karedath
    • , Xin Chen
    • , Sinjinee Sardar
    • , Kyungsuk Yum
    • , Gyu Leem
    • , Brad S. Pierce
    • , Kwangho Nam
    • , Jiali Gao
    •  & Junha Jeon

Amendments & Corrections