Associate Editor highlight – interview with Professor Jinlong Gong

In 2021, Chemical Science was delighted to welcome Professor Jinlong Gong as an Associate Editor, handling manuscripts within the area of heterogenous catalysis. To celebrate this occasion, we met virtually with Jinlong to discuss his research and to discuss the kind of manuscripts that he is looking forward to handling for the journal.

Jinlong’s research focuses on understanding the catalytic processes occurring during alkane dehydrogenation and CO2 hydrogenation by developing advanced catalytic materials, as well as optimised industrial processes.

What excites you most about your area of research and what has been the most exciting moment of your career so far?

The major motivation of my research is to provide constructive solutions for a sustainable society, particularly associated with the chemical industry. For example, propane dehydrogenation is a traditional chemical process which has been under development over the past 60-80 years. Our research therefore focuses on trying to develop new catalytic processes to reduce the energy consumption with enhanced catalytic performance. Another example is about the utilisation of CO2 with sustainable energy to produce renewable fuels and help reduce emissions. President Xi Jinping has announced that China’s aim is to achieve a carbon neutral society by 2060. Actually, my work on photocatalytic reduction of CO2 follows such a direction. The big challenge in this area is to improve the efficiency, which is currently still low.

Some of the most exciting moments of my career have been when former students of mine have been recruited into faculty positions at top universities. It is always a pleasure to see young researchers grow up independently and then go on to do amazing things! Another exciting moment for me was when we were able to find new oxide materials that displayed very high efficiency for propane dehydrogenation. We believe that this is going to be the next generation of catalysts for this process.

What has been the most challenging moment of your career so far?

It is always challenging to navigate research into a scientifically critical direction at the right time, rather than staying in a comfortable zone. Transitioning the direction of your research into a new but important area tends be exhausting, especially at the start. On the other hand, the potential reward can be more exciting. Sometimes, it is also challenging to convince funders to support an unrevealed but potentially important research direction, which can be a common issue for most scientists.

You have published over 10 papers with Chemical Science since your first publication with us in 2015. Of these papers, which one do you feel has made the most significant contribution to your area of research and why?

One of the pieces that I like the most is a paper that we published in 2019 – hydroxyl-mediated ethanol selectivity of CO2 hydrogenation. In this paper, we developed a catalyst based on Rh, where we simply added some Fe and Li metals as promoters. One interesting thing we found was that, with various oxide supports, we can tune the surface coverage of hydroxyl groups bound on Rh-based catalysts, which has a very important correlation with ethanol selectivity for CO2 hydrogenation. I believe that this story will provide researchers with a deeper understanding of the formation mechanism of ethanol on this kind of catalyst, particularly in understanding the C-C coupling mechanism for this reaction, which is very important if we want to have a high C2 selectivity.

It’s been over a year after China’s first lockdown started. What changes have you witnessed in the Chinese researcher community? Do you think there are any new challenges or opportunities for chemistry researchers from this ongoing global pandemic?

This is a very good question! Last spring, early in the pandemic, many online seminars were arranged by researchers from all over the world and involved various publishers, which was great for scientific communication. In terms of academic activities, I noticed that there weren’t any big delays in the publication process, which again was great. Since last fall, the situation in China has become much better, with most academic meetings now being able to take place on-site.

One noticeable opportunity from the overall research strategy in China is the focus on health. Funding agencies will now put even more emphasis on bio-relevant research. I think there will be a big boom in this area in China in the next few decades. Globally, I believe we will see lots of joint projects taking place between research groups that work in chemical engineering, chemistry, materials and medicine, which will promote multidisciplinary collaboration.

Why do you feel that researchers should choose to publish their work in Chemical Science

Chemical Science, as flagship journal of the Royal Society of Chemistry, has a prestigious reputation in the chemistry and physical science community. Chemical Science publishes cutting-edge papers that provide deep and novel understanding of the chemistry of important reactions. Multidisciplinary research, including radical physical chemistry, is also welcome. For example, AI methods used to screen candidate materials or analyse chemical reactions can be attractive. This kind of research, in turn, will reward the scientific community. Chemical Science, as an open-access journal, provides a highly fair publishing platform, and the Editorial Office is also very efficient – manuscripts are turned around in a very timely manner. It is one of best journals publishing chemical research.

What attracted you to join the Editorial Board of Chemical Science?

I have served on the Advisory Board for Chemical Science since 2013, and I am also a regular referee for the journal. Now, I feel that I am very fortunate to have the opportunity to handle submissions to Chemical Science, particularly in the area of heterogeneous catalysis. Chemical Science has a high-profile impact on the scientific community, which provides me with the opportunity to handle exciting scientific research, communicate with diverse groups of scientists, and most importantly, serve the research community. Together with the warm editorial team, we can provide authors with a professional publication experience.

It is important for Chemical Science to have an open and inclusive Editorial Board. Do you feel that we are achieving this goal?

I received a lot of warm greetings when May introduced me to the other members of the Editorial Board. Looking at the profiles of our members in the editorial team, we have great diversity among the board, including Associate Editors from all over the world, with expertise spanning across the chemical sciences. So far, I think we are achieving the goal. They are all renowned scientists.

What impact do you feel that your area of research can make over the next 10 years?

First of all, I would like to highlight the impact that I feel light alkane dehydrogenation can make in the next 10 years. This is a major industrial process to produce ethylene/propylene, which are building blocks for preparing polymers. The development of new technology as well as catalytic materials will further decrease the energy consumption during this process, and also increase the catalytic efficiency overall. This can help to ensure a better and greener industrial process in the future.

My second area of research focuses on the photocatalytic reduction of CO2. It’s very important for us to transform from a fossil fuel society into a renewable energy society. Energy conversion and storage technologies will play critical roles in this area. In the next 10-20 years, I think this type of research will definitely have more impact. There has already been a lot of investment into the research as well as infrastructure to support this initiative, so I hope that this goal will be able to be realised.

Submit to Chemical Science today! Check out our author guidelines for information on our article types or find out more about the advantages of publishing in a Royal Society of Chemistry journal.

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Chemical Science HOT Articles: April 2021

New month, new HOT articles!

We are pleased to share a selection of our referee-recommended HOT articles for April 2021. We hope you enjoy reading these articles, congratulations to all the authors whose articles are featured! As always, Chemical Science is free to read & download.

You can explore our full 2021 Chemical Science HOT Article Collection here!

 

Browse a selection of our April HOT articles below:

Reaction-based machine learning representations for predicting the enantioselectivity of organocatalysts
Simone Gallarati, Raimon Fabregat, Rubén Laplaza, Sinjini Bhattacharjee, Matthew D. Wodrich and Clemence Corminboeuf
Chem. Sci., 2021, Advance Article

Deaminative meta-C–H alkylation by ruthenium(ii) catalysis
Wen Wei, Hao Yu, Agnese Zangarelli and Lutz Ackermann
Chem. Sci., 2021, Advance Article

Prediction and mitigation of mutation threats to COVID-19 vaccines and antibody therapies
Jiahui Chen, Kaifu Gao, Rui Wang and Guo-Wei Wei
Chem. Sci., 2021, Advance Article

Recent advances in single atom catalysts for the electrochemical carbon dioxide reduction reaction
Jincheng Zhang, Weizheng Cai, Fang Xin Hu, Hongbin Yang and Bin Liu
Chem. Sci., 2021, Advance Article

Wavy graphene sheets from electrochemical sewing of corannulene
Carlo Bruno, Eleonora Ussano, Gianni Barucca, Davide Vanossi, Giovanni Valenti, Edward A. Jackson, Andrea Goldoni, Lucio Litti, Simona Fermani, Luca Pasquali, Moreno Meneghetti, Claudio Fontanesi, Lawrence T. Scott, Francesco Paolucci and Massimo Marcaccio
Chem. Sci., 2021, Advance Article

Oxidative additions of alkynyl/vinyl iodides to gold and gold-catalyzed vinylation reactions triggered by the MeDalphos ligand
Jessica Rodriguez, Alexis Tabey, Sonia Mallet-Ladeira and Didier Bourissou
Chem. Sci., 2021, Advance Article

 

Chemical Science, Royal Society of Chemistry

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Chemical Science welcomes new Associate Editor Hemamala Karunadasa

We wish a very warm welcome to our new Chemical Science Associate Editor Hemamala Karunadasa!

Hemamala Karunadasa Chemical Science Associate Editor

 

Hemamala Karunadasa is an Associate Professor of Chemistry at Stanford University and a Faculty Scientist at the SLAC National Lab. Her group is invested in gaining synthetic control over extended ionic solids, with a focus on halide perovskites. They seek to both improve technologically important materials as well as to design new materials with unprecedented properties.

Hemamala was born in Sri Lanka and attended school in Colombo. She studied solid-state chemistry at Princeton University, receiving her A.B. in 2003. She moved to molecular inorganic chemistry for my Ph.D., which she received from UC Berkeley in 2009, and for her postdoctoral studies at the Lawrence Berkeley National Lab and at the California Institute of Technology.

As an associate editor, Hemamala looks forward to receiving papers that provide fundamental insights into obtaining desirable properties from new materials.

 

Browse a selection of Hemamala’s work below:

Dimensional reduction of the small-bandgap double perovskite Cs2AgTlBr6
Bridget A. Connor, Raisa-Ioana Biega, Linn Leppert and Hemamala I. Karunadasa
Chem. Sci., 2020, 11, 7708-7715
DOI: 10.1039/D0SC01580F, Edge Article

A pencil-and-paper method for elucidating halide double perovskite band structures
Adam H. Slavney, Bridget A. Connor, Linn Leppert and Hemamala I. Karunadasa
Chem. Sci., 2019, 10, 11041-11053
DOI: 10.1039/C9SC03219C, Edge Article

Tuning the bandgap of Cs2AgBiBr6 through dilute tin alloying
Kurt P. Lindquist, Stephanie A. Mack, Adam H. Slavney, Linn Leppert, Aryeh Gold-Parker, Jonathan F. Stebbins, Alberto Salleo, Michael F. Toney, Jeffrey B. Neaton and Hemamala I. Karunadasa
Chem. Sci., 2019, 10, 10620-10628
DOI: 10.1039/C9SC02581B, Edge Article

Structural origins of broadband emission from layered Pb–Br hybrid perovskites
Matthew D. Smith, Adam Jaffe, Emma R. Dohner, Aaron M. Lindenberg and Hemamala I. Karunadasa
Chem. Sci., 2017, 8, 4497-4504
DOI: 10.1039/C7SC01590A, Edge Article

 

Chemical Science, Royal Society of Chemistry

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Chemical Science HOT Articles: March 2021

New month, new HOT articles!

We are pleased to share a selection of our referee-recommended HOT articles for March 2021. We hope you enjoy reading these articles, congratulations to all the authors whose articles are featured! As always, Chemical Science is free to read & download.

You can explore our full 2021 Chemical Science HOT Article Collection here!

 

Browse a selection of our March HOT articles below:

Photoactive electron donor–acceptor complex platform for Ni-mediated C(sp3)–C(sp2) bond formation
Lisa Marie Kammer, Shorouk O. Badir, Ren-Ming Hu and Gary A. Molander
Chem. Sci., 2021, Advance Article

Exploiting host–guest chemistry to manipulate magnetic interactions in metallosupramolecular M4L6 tetrahedral cages
Aaron J. Scott, Julia Vallejo, Arup Sarkar, Lucy Smythe, E. Regincós Martí, Gary S. Nichol, Wim T. Klooster, Simon J. Coles, Mark Murrie, Gopalan Rajaraman, Stergios Piligkos, Paul J. Lusby and Euan K. Brechin
Chem. Sci., 2021, Advance Article

DNA-based constitutional dynamic networks as functional modules for logic gates and computing circuit operations
Zhixin Zhou, Jianbang Wang, R. D. Levine, Francoise Remacle and Itamar Willner
Chem. Sci., 2021, Advance Article

Asymmetric synthesis of dihydro-1,3-dioxepines by Rh(ii)/Sm(iii) relay catalytic three-component tandem [4 + 3]-cycloaddition
Chaoran Xu, Jianglin Qiao, Shunxi Dong, Yuqiao Zhou, Xiaohua Liu and Xiaoming Feng
Chem. Sci., 2021, Advance Article

Targeted 1,3-dipolar cycloaddition with acrolein for cancer prodrug activation
Ambara R. Pradipta, Peni Ahmadi, Kazuki Terashima, Kyohei Muguruma, Motoko Fujii, Tomoya Ichino, Satoshi Maeda and Katsunori Tanaka
Chem. Sci., 2021, Advance Article

Three-membered cyclic digermylenes stabilised by an N-heterocyclic carbene
Zhaowen Dong, Jan Mathis Winkler, Marc Schmidtmann and Thomas Müller
Chem. Sci., 2021, Advance Article

 

Chemical Science, Royal Society of Chemistry

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Gearing up for motion in ruthenium rotors

The mighty gear is essential in machines. Even when scaling down the size of the machine, like from cars to small wristwatches, gears are necessary to transmit motion and mechanical power across the system. Machines can be decreased in size all the way to the nanoscale with molecular machines, where individual molecules can produce mechanical motion in response to external stimuli. Just as in macroscopic machines (e.g. cars), the addition of gears to nanomachines is needed for creating more complex assemblies with controlled motion, extending the applications of these molecules beyond the fundamental.

Figure 1. A schematic representation of the design for trains of molecular gears.

A team of researchers from France and Japan have now reported a series of molecular gears, with the aim of achieving correlated motion within trains of gears across a surface (Figure 1). To achieve this correlated motion, the researchers designed desymmetrised organometallic molecular gears based around star-shaped ruthenium piano-stool complexes. These molecular gears incorporated a facially capping hydrotris(indazolyl)borate ligand at one end, which both anchors the complex to the surface and lifts the central metal centre away to enable a rotational axis around the ruthenium. At the other end, the molecular gears have a cyclopentadienyl core to act as the cogwheel, functionalised with bulky groups that mimic the teeth that allow correlated motion between the gears (Figure 2). The researchers set out to make these molecular gears with lower symmetry to allow for detailed on-surface mechanical studies, by changing one of the five teeth (i.e. the functionalised groups around the cyclopentadienyl core) to include a steric or chemical tag– this is shown in Figures 1 and 2 by the green section.

Figure 2. Chemical structure of the molecular gears, with the anchoring ligand in black beneath the ruthenium centre and the rotating cogwheel cyclopentadienyl ligand in blue. The rectangles represent the teeth of the cogwheel as the bulky groups added to the central cyclopentadienyl core, where one of the five teeth (coloured green rather than blue) is sterically or chemically changed to lower the symmetry.

The researchers developed a modular synthetic approach to achieve desymmetrisation of the star-shaped ruthenium molecular gears, based on post-functionalisation of the central cyclopentadienyl core with Ni(II) porphyrins to act as the teeth of the cogwheels. They used an unsymmetrical 1,2,3,4,5-penta(p-halogenophenyl)cyclopentadienyl as the core; the p-halogenophenyl groups are all pre-activated to allow for further functionalisation, but one of the five is a p-iodophenyl group that chemoselectively reacts over the other four p-bromophenyl groups. Scheme 1 shows a sequential synthetic route towards one of the desymmetrised molecular gears: the p-iodophenyl group is first functionalised with a unique porphyrin (shown in green), before subsequent functionalisation of the four other p-bromophenyl groups with the same porphyrins (shown in blue), all using palladium-catalysed cross-coupling reactions.

Synthetic scheme showing the route towards the desymmetrised molecular gears

Scheme 1. An example synthetic route towards desymmetrised molecular This example shows a sterically tagged cogwheel, where the unique porphyrinic tooth (in green) contains a longer linker than the four other teeth (in blue).

The researchers varied their approach to changing the unique porphyrinic tooth for the molecular gear, using either steric tagging (with one longer linker between the porphyrin and p-halogenophenyl group) or chemical tagging, using either one distinct electron-deficient porphyrin (achieved by using p-cyanophenyl substituents on the tetrapyrrole core) or one distinct metal porphyrin (Zn(II) instead of Ni(II)). The synthesised desymmetrised molecular gears were characterised using spectroscopic and electrochemical techniques, and the researchers are currently undertaking further mechanical studies to understand the correlated motion of these gears on surfaces.

 

To find out more, please read:

Desymmetrised pentaporphyrinic gears mounted on metallo-organic anchors

Seifallah Abid, Yohan Gisbert, Mitsuru Kojima, Nathalie Saffon-Merceron, Jérôme Cuny, Claire Kammerer* and  Gwénaël Rapenne*

Chem. Sci., 2021, Advance Article

 

About the blogger:

Photograph of the author, Samantha AppsDr. Samantha Apps recently finished her post as a Postdoctoral Research Associate in the Lu Lab at the University of Minnesota, USA, and obtained her PhD in 2019 from Imperial College London, UK. She has spent the last few years, both in her PhD and postdoc, researching synthetic nitrogen fixation and transition metal complexes that can activate and functionalise dinitrogen. Outside of the lab, you’ll likely find her baking at home, where her years of synthetic lab training has sparked a passion in kitchen chemistry too.

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Chemical Science HOT Articles: February 2021

New month, new HOT articles!

We are pleased to share a selection of our referee-recommended HOT articles for February 2021. We hope you enjoy reading these articles, congratulations to all the authors whose articles are featured! As always, Chemical Science is free to read & download.

You can explore our full 2021 Chemical Science HOT Article Collection here!

 

Browse a selection of our February HOT articles below:

Towards the rational design of ylide-substituted phosphines for gold(i)-catalysis: from inactive to ppm-level catalysis
Jens Handelmann, Chatla Naga Babu, Henning Steinert, Christopher Schwarz, Thorsten Scherpf, Alexander Kroll and Viktoria H. Gessner;
Chem. Sci., 2021, Advance Article

Ruthenium-catalyzed formal sp3 C–H activation of allylsilanes/esters with olefins: efficient access to functionalized 1,3-dienes
Dattatraya H. Dethe, Nagabhushana C. Beeralingappa, Saikat Das and Appasaheb K. Nirpal
Chem. Sci., 2021, Advance Article

Symmetry-related residues as promising hotspots for the evolution of de novo oligomeric enzymes
Jaeseung Yu, Jinsol Yang, Chaok Seok and Woon Ju Song
Chem. Sci., 2021, Advance Article

Desymmetrised pentaporphyrinic gears mounted on metallo-organic anchors
Seifallah Abid, Yohan Gisbert, Mitsuru Kojima, Nathalie Saffon-Merceron, Jérôme Cuny, Claire Kammerer and Gwénaël Rapenne
Chem. Sci., 2021, Advance Article

The atomic-level regulation of single-atom site catalysts for the electrochemical CO2 reduction reaction
Qingyun Qu, Shufang Ji, Yuanjun Chen, Dingsheng Wang and Yadong Li
Chem. Sci., 2021, Advance Article

Chemical tuning of spin clock transitions in molecular monomers based on nuclear spin-free Ni(ii)
Marcos Rubín-Osanz, François Lambert, Feng Shao, Eric Rivière, Régis Guillot, Nicolas Suaud, Nathalie Guihéry, David Zueco, Anne-Laure Barra, Talal Mallah and Fernando Luis
Chem. Sci., 2021, Advance Article
Chemical Science, Royal Society of Chemistry

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Associate Editor highlight – interview with Professor Ning Jiao

Ning Jiao, Chemical Science Associate Editor

In 2021, Chemical Science was delighted to welcome Professor Ning Jiao as an Associate Editor, handling manuscripts within the area of organic synthesis. To celebrate this occasion, we met virtually with Ning to discuss his area of research and what he hopes to achieve through his new role with the journal.

Ning’s research focuses on new methodology development in synthetic chemistry. His group mainly focus on heteroatom incorporation reactions, such as oxygenation, nitrogenation and halogenation reactions towards the synthesis and discovery of functional molecules.

What excites you most about your area of research and what has been the most exciting moment of your career so far?

In contrast to well-developed C-C bond forming reactions, selective C-C bond cleavage is still one of the biggest challenges in organic chemistry, and is highly attractive because it can bring innovative solutions to a number of different applications including coal liquefaction, petroleum cracking, polymer degradation, and biomass conversion.

One of the most exciting moments of my career was when we were able to achieve inert C-C bond activation. Following on from this, we have developed some novel C-C bond functionalisation reactions over the past 10 years through selective inert C-C, C=C and C≡C bond cleavage. We have successfully incorporated nitrogen and/or oxygen atoms into a variety of starting materials, even very simple hydrocarbons, producing some interesting value added nitrogen- or oxygen-containing compounds. I therefore really like this area of research.

What has been the most challenging moment of your career so far?

The most challenging moments for me have been when the results we obtain are not necessarily the same as what we expected, which has happened at various times throughout my research career. The challenge is that you must be able to clearly explain what happened for this new chemistry. It can be incredibly challenging to fully understand and prove new mechanisms, because sometimes you aren’t always able to isolate the active intermediate so therefore can’t always monitor the real reaction process. I have been really challenged by mechanistic studies in my career, but I have learnt to look for answers in detailed studies of the by-products and in the in-situ detection of intermediates. I’ve also learnt to verify the answers obtained through the design of new reactions.

What is your favourite reaction and why?

My favourite reactions are those which are easily operated under mild and environmentally friendly conditions, and can turn waste into value materials. In my opinion, if somebody can use carbon dioxide as the oxygen source for the preparation of oxygen-containing compounds, with the release of carbon monoxide as a by-product that can then be used as an energy source, then this would be one of my favourite ideal reactions that I would like to realise.

Which of your Chemical Science publications are you most proud of and why?

I definitely love every paper that we have published in Chemical Science, and I am especially proud of our publications over the last two years. These have provided contributions to the area of C-C bond functionalization reactions, in which we have achieved the incorporation of oxygen and nitrogen atoms into molecules through C-C and C=C bond cleavage, respectively, for the preparation of tertiary amines and cyclic imides. The one that I am most proud of will be our next publication in Chemical Science!

Chemical Science was delighted to welcome you to the Editorial Board in 2021. What are you most looking forward to when acting as Associate Editor for the journal?

Thank you! It was my great pleasure to take on this new role. We know that Chemical Science is one of the top multidisciplinary chemistry journals, being the flagship journal of the Royal Society of Chemistry. It is also one of the few top journals that is fully open access with all articles being free to read, and free to publish. This is very attractive and gives the journal very strong vitality. As an Associate Editor, I’m so delighted to be able to contribute to the journal with the rest of the Editorial Board members to help to continue to make Chemical Science the most progressive, exciting and impactful leading chemistry journal. I also hope to serve all authors and readers as well as I can with optimal publication times.

One other aspect of the role that I am highly excited about is having the opportunity to learn and read the latest research first hand, and to learn more about the various contributions and novel ideas that come out from the organic community.

What goal would you set for yourself over the next 10 years?

I have several goals for my research. I first hope that we can realise the direct transformation of carbon dioxide as an oxygen source in oxygenation reactions. I would also like to realise direct catalytic nitrogen-containing compound synthesis, using nitrogen gas as the nitrogen source under mild conditions. Overall, my biggest goal is to apply our methods for the efficient synthesis and discovery of drugs and other functional molecules, and to make contributions to the development of green and sustainable chemistry.

In celebration of joining the Chemical Science team, Ning has highlighted a selection of important organic chemistry contributions from the past few years. The collection can be viewed here.

Submit to Chemical Science today! Check out our author guidelines for information on our article types or find out more about the advantages of publishing in a Royal Society of Chemistry journal.

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Methylene in the middle: from Zn to Ti

Methylene (-CH2) is one of the simplest and most important building blocks for chemical synthesis. Methylenation reactions add methylene groups to molecules and often proceed using transition metal methylene complexes. Titanium methylene complexes are excellent for methylenations and have been used in a variety of reactions such as olefin metathesis, polymerisations or olefination of carbonyls. Early examples of such titanium methylenation reagents include Tebbe’s reagent that can generate a terminally bound mononuclear titanium methylidene, Cp2Ti=CH2 (Figure 1a), or a methylenation reagent prepared from CH2Br2, Zn and TiCl4 (with catalytic lead), referred to as ‘CH2X2-Zn(Pb)-TiCl4’.

Figure 1. (a) The titanium methylidene methylenating reagent from the Tebbe or Petasis reagents. (b) The first key step for the ‘CH2X2-Zn(Pb)-TiCl4’ methylenating reagent: generation of the zinc methylene. (c) The second key step for ‘CH2X2-Zn(Pb)-TiCl4’ methylenating reagent: reduction of Ti(IV) to Ti(III).

Researchers from Japan have been interested in the ‘CH2X2-Zn(Pb)-TiCl4’ methylenation reagent and in particular, deducing the molecular structure of the reactive species. Earlier studies have revealed two key steps in the preparation of this methylenating reagent: the first is that a zinc methylene species, ‘CH2(ZnX2)’, is formed by the reaction of CH2X2 with Zn and catalytic lead (Figure 1b), and the second is that the Ti(IV) chloride reagent is reduced to Ti(III) chloride by Zn(0) simultaneously (Figure 1c). The researchers hypothesised that a reactive titanium methylidene species (similar to that generated from Tebbe’s reagent in Figure 1a) should form via a transmetallation event between the zinc methylene species and the Ti(III) chloride, and thus be the reactive methylenating species of the ‘CH2X2-Zn(Pb)-TiCl4’ methylenation reagent.

Scheme 1. The synthesis of the titanium methylene complex 3 generated via transmetallation.

To confirm their hypothesis, the researchers studied the reactivity of multiple combinations of a zinc methylene species (1) and titanium(III or IV) chloride reagents, with and without additional ligands (such as phosphines, amines or ethers). The researchers found that most combinations of reagents resulted in methylene loss via the generation of methane or ethylene, but the combination of TMEDA adducts of the zinc methylene (1a) and Ti(III) chloride (2) gave clean conversion to a new titanium methylene species 3 (Scheme 1). Although the researchers originally hypothesised the formation of a mononuclear titanium methylidene via methylene transmetallation from zinc to titanium, the new species 3 was revealed to be a dinuclear, bridging methylene complex. The dinuclear species was characterised using NMR spectroscopy and single-crystal X-ray diffraction techniques, and the connectivity of the bridging methylene was conclusively established by the X-ray crystal structure.

After elucidating the structure of the dinuclear titanium methylene complex, the researchers tested 3 as a methylenating reagent and observed successful methylene transfer reactions from 3 to esters, terminal olefins and 1,3-dienes. A further computational mechanistic study for the reactivity of 3 and a 1,3-diene was performed, where the DFT calculations indicated a mononuclear titanium methylidene as the reactive species, generated from the dinuclear titanium methylene complex. These calculations corroborate the researchers’ initial hypothesis and correlate with Tebbe’s reagent, where the reactive methylenating agent is also a mononuclear titanium methylidene that is generated from a dinuclear bridging methylene complex.

 

To find out more, please read:

Structural elucidation of a methylenation reagent of esters: synthesis and reactivity of a dinuclear titanium(III) methylene complex

Takashi Kurogi,* Kaito Kuroki, Shunsuke Moritani and Kazuhiko Takai*

Chem. Sci., 2021, Advance Article

 

About the blogger:

Photograph of the author, Samantha AppsDr. Samantha Apps recently finished her post as a Postdoctoral Research Associate in the Lu Lab at the University of Minnesota, USA, and obtained her PhD in 2019 from Imperial College London, UK. She has spent the last few years, both in her PhD and postdoc, researching synthetic nitrogen fixation and transition metal complexes that can activate and functionalise dinitrogen. Outside of the lab, you’ll likely find her baking at home, where her years of synthetic lab training has sparked a passion in kitchen chemistry too.

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Chemical Science HOT Articles: January 2021

New year, new HOT article collection!

We are pleased to share a selection of our referee-recommended HOT articles for January 2021. We hope you enjoy reading these articles and congratulations to all the authors whose articles are featured! As always, Chemical Science is free to read & download.

You can explore our full 2021 Chemical Science HOT Article Collection here!

 

Browse a selection of our January HOT articles below:

Directed evolution of cyclic peptides for inhibition of autophagy
Joshua P. Gray, Md. Nasir Uddin, Rajan Chaudhari, Margie N. Sutton, Hailing Yang, Philip Rask, Hannah Locke, Brian J. Engel, Nefeli Batistatou, Jing Wang, Brian J. Grindel, Pratip Bhattacharya, Seth T. Gammon, Shuxing Zhang, David Piwnica-Worms, Joshua A. Kritzer, Zhen Lu, Robert C. Bast, Jr. and Steven W. Millward
Chem. Sci., 2021, Advance Article

Conformational analysis by UV spectroscopy: the decisive contribution of environment-induced electronic Stark effects
Jeremy Donon, Sana Habka, Michel Mons, Valérie Brenner and Eric Gloaguen
Chem. Sci., 2021, Advance Article

Identifying key mononuclear Fe species for low-temperature methane oxidation
Tao Yu, Zhi Li, Wilm Jones, Yuanshuai Liu, Qian He, Weiyu Song, Pengfei Du, Bing Yang, Hongyu An, Daniela M. Farmer, Chengwu Qiu, Aiqin Wang, Bert M. Weckhuysen, Andrew M. Beale and Wenhao Luo
Chem. Sci., 2021, Advance Article

A feasible approach for automatically differentiable unitary coupled-cluster on quantum computers
Jakob S. Kottmann, Abhinav Anand and Alán Aspuru-Guzik
Chem. Sci., 2021, Advance Article

A photoswitchable strapped calix[4]pyrrole receptor: highly effective chloride binding and release
David Villarón, Maxime A. Siegler and Sander J. Wezenberg
Chem. Sci., 2021, Advance Article

Controlling multiple orderings in metal thiocyanate molecular perovskites Ax{Ni[Bi(SCN)6]}
Jie Yie Lee, Sanliang Ling, Stephen P. Argent, Mark S. Senn, Laura Cañadillas-Delgado and Matthew J. Cliffe
Chem. Sci., 2021, Advance Article

Structural elucidation of a methylenation reagent of esters: synthesis and reactivity of a dinuclear titanium(iii) methylene complex
Takashi Kurogi, Kaito Kuroki, Shunsuke Moritani and Kazuhiko Takai
Chem. Sci., 2021, Advance Article
Chemical Science, Royal Society of Chemistry

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Chemical Science welcomes new Associate Editor Jinlong Gong

Jinlong Gong, Chemical Science Associate Editor

We wish a very warm welcome to our new Chemical Science Associate Editor Jinlong Gong!

 

Jinlong Gong studied chemical engineering and received his B.S. and M.S. degrees from Tianjin University and his Ph.D. from the University of Texas at Austin. Upon the completion of postdoctoral research at Harvard University, he joined the faculty of chemical engineering at Tianjin University, where he currently holds a Pei Yang Chair Professorship.

His research group work on heterogeneous catalysis and kinetics with a focus on catalytic conversions of small molecules, production of hydrogen energy, and syntheses and applications of nanostructured catalytic materials.

 

Browse a selection of Jinlong’s work below:

Facilitating the reduction of V–O bonds on VOx/ZrO2 catalysts for non-oxidative propane dehydrogenation
Yufei Xie, Ran Luo, Guodong Sun, Sai Chen, Zhi-Jian Zhao, Rentao Mu and Jinlong Gong
Chem. Sci., 2020, 11, 3845-3851
DOI: 10.1039/D0SC00690D, Edge Article

Gas–water interface engineered exceptional photoconversion of fatty acids to olefins
Qin Dai, Jingyi Lin, Hongbin Cao, He Zhao, Guangfei Yu, Chaoqun Li, Tianyu Wang, Yanchun Shi, Guangwei Wang and Jinlong Gong
Green Chem., 2020, 22, 7848-7857
DOI: 10.1039/D0GC02237C, Paper

Theoretical insights into single-atom catalysts
Lulu Li, Xin Chang, Xiaoyun Lin, Zhi-Jian Zhao and Jinlong Gong
Chem. Soc. Rev., 2020, 49, 8156-8178
DOI: 10.1039/D0CS00795A, Review Article

Operando characterization techniques for electrocatalysis
Jingkun Li and Jinlong Gong
Energy Environ. Sci., 2020, 13, 3748-3779
DOI: 10.1039/D0EE01706J, Review Article

Core–shell structured catalysts for thermocatalytic, photocatalytic, and electrocatalytic conversion of CO2
Sonali Das, Javier Pérez-Ramírez, Jinlong Gong, Nikita Dewangan, Kus Hidajat, Bruce C. Gates and Sibudjing Kawi
Chem. Soc. Rev., 2020, 49, 2937-3004
DOI: 10.1039/C9CS00713J, Review Article

Chemical Science, Royal Society of Chemistry

Submit to Chemical Science today! Check out our author guidelines for information on our article types or find out more about the advantages of publishing in a Royal Society of Chemistry journal.

Keep up to date with our latest articles, reviews, collections & more by following us on Twitter. You can also keep informed by signing up to our E-Alerts.

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