Potassium teter-butoxide Strikes Again!

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C–H carboxylation of heteroarenes with ambient CO₂

Sabine Fenner^a and   Lutz Ackermann*^a  

Green Chem., 2016, Advance Article

The C–H carboxylation of heteroarenes was achieved under transition metal-free reaction conditions with naturally abundant CO₂ as the C1 source at relatively low temperature. The C–H carboxylation was mediated by KOt-Bu at atmospheric pressure of CO₂, and thereby provided atom- and step-economical access to various heteroaromatic carboxylic acid derivatives.

Love at second sight for CO2 and H2

  http://www.sciencemag.org/content/350/6261/629.summary

 

Science 6 November 2015:
Vol. 350 no. 6261 pp. 629-630
DOI: 10.1126/science.aac7997

Love at second sight for CO₂ and H₂ in organic synthesis

1. Jürgen Klankermayer,
2. Walter Leitner

+ Author Affiliations

1. Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, 52074 Aachen, Germany.

1. E-mail: jklankermayer@itmc.rwth-aachen.de; leitner@itmc.rwth-aachen.de

Many romantic comedies are based on a couple with opposite personalities who fall in love, lose track of each other, and reunite against all odds, most often with the help of a mediator. This cinematic scenario recaps the recent progress in bringing together two molecular actors, carbon dioxide (CO₂) and hydrogen (H₂), with the help of homogeneous catalysts in solution. Of the pair, CO₂ is the reluctant partner; it is thermodynamically very stable and kinetically inert in typical organic syntheses. However, an energetic partner such as H₂ can bring out its reactivity if their combination is properly directed. Organometallic catalysts have recently opened new possibilities to merge this odd couple of CO₂ and H₂ and, with the support of helpful in-laws (co-reactants), to establish synthetic methods for sustainable chemical processes across the chemical value chain.

Progress in Synthesis of Highly Active and Stable Nickel-Based Catalysts for Carbon Dioxide Reforming of Methane

Prof. Sibudjing Kawi, Dr. Yasotha Kathiraser, Dr. Jun Ni, Dr. Usman Oemar, Dr. Ziwei Li, Dr. Eng Toon Saw

Abstract

In recent decades, rising anthropogenic greenhouse gas emissions (mainly CO₂ and CH₄) have increased alarm due to escalating effects of global warming. The dry carbon dioxide reforming of methane (DRM) reaction is a sustainable way to utilize these notorious greenhouse gases. This paper presents a review of recent progress in the development of nickel-based catalysts for the DRM reaction. The enviable low cost and wide availability of nickel compared with noble metals is the main reason for persistent research efforts in optimizing the synthesis of nickel-based catalysts. Important catalyst features for the rational design of a coke-resistant nickel-based nanocatalyst for the DRM reaction are also discussed. In addition, several innovative developments based on salient features for the stabilization of nickel nanocatalysts through various means (which include functionalization with precursors, synthesis by plasma treatment, stabilization/confinement on mesoporous/microporous/carbon supports, and the formation of metal oxides) are highlighted. The final part of this review covers major issues and proposed improvement strategies pertaining to the rational design of nickel-based catalysts with high activity and stability for the DRM reaction.

http://onlinelibrary.wiley.com/doi/10.1002/cssc.201500390/full

A Highly Efficient Heterogenized Iridium Complex for the Catalytic Hydrogenation of Carbon Dioxide to Formate

A Highly Efficient Heterogenized Iridium Complex for the Catalytic Hydrogenation of Carbon Dioxide to Formate (pages 3410–3413)
Kwangho Park, Gunniya Hariyanandam Gunasekar , Natarajan Prakash, Dr. Kwang-Deog Jung and Prof. Dr. Sungho Yoon
Article first published online: 25 AUG 2015 | DOI: 10.1002/cssc.201500436

Complex in New Basket: A new, highly porous, industrially viable, heterogenized Ir catalyst has been synthesized and characterized, and the coordination environment is confirmed to be similar to that of its homogeneous counterpart. The catalyst efficiently converts CO₂ to formate through hydrogenation at high turnover frequencies (TOFs) and turnover numbers (TONs) and shows good stability during the recycling process.

Abstract

A heterogenized catalyst on a highly porous covalent triazine framework was synthesized and characterized to have a coordination environment similar to that of its homogeneous counterpart. The catalyst efficiently converted CO₂ into formate through hydrogenation with a turnover number of 5000 after 2 h and an initial turnover frequency of up to 5300 h⁻¹; both of these values are the highest reported to date for a heterogeneous catalyst, which makes it attractive toward industrial application. Furthermore, the synthesized catalyst was found to be stable in air and was recycled by simple filtration without significant loss of catalytic activity.
 

http://onlinelibrary.wiley.com/doi/10.1002/cssc.201500436/full