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Organometallics in catalysis: an article collection

Perhaps the most well-known applications of organometallics in catalysis are the Ziegler–Natta catalysts which are used to generate polymers; the catalysts are made up of mixtures of transition metal halides and organo-aluminium complexes. Karl Ziegler and Giulio Natta were awarded the 1963 Nobel Prize in Chemistry for their discovery and development of the catalysts, which today are the most commonly used catalysts for the manufacture of polythene.

The esteemed history of organometallics is not to be under-estimated and includes Grignard’s reagents, the Heck reaction, Schrock catalysts, Grubbs’ catalysts and the Suzuki Coupling to name just a few. Organometallic compounds have revolutionised science and industry and to keep you up to date with the latest break-through research being made across all areas of organometallics in catalysis, we have made this cross-journal article collection free until 26th September.

Organometallic hydrogen transfer and dehydrogenation catalysts for the conversion of bio-renewable alcohols, Andrew C. Marr, Catal. Sci. Technol., 2012, 2, 279-287

Synthesis of functionalized thiophenes and oligothiophenes by selective and iterative cross-coupling reactions using indium organometallics, M. Montserrat Martínez, Miguel Peña-López, José Pérez Sestelo and Luis A. Sarandeses, Org. Biomol. Chem., 2012, 10, 3892-3898

Homogeneous and heterogeneous catalysts for multicomponent reactions, Maria José Climent, Avelino Corma and Sara Iborra, RSC Adv., 2012, 2, 16-58

Amine directed Pd(II)-catalyzed C–H bond functionalization under ambient conditions, Benjamin Haffemayer, Moises Gulias and Matthew J. Gaunt, Chem. Sci., 2011, 2, 312-315

Metal–ligand bifunctional activation and transfer of N–H bonds, Kilian Muñiz, Anton Lishchynskyi, Jan Streuff, Martin Nieger, Eduardo C. Escudero-Adán and Marta Martínez Belmonte, Chem. Commun., 2011, 47, 4911-4913

Symmetrical and unsymmetrical pincer complexes with group 10 metals: synthesis via aryl C–H activation and some catalytic applications, Jun-Long Niu, Xin-Qi Hao, Jun-Fang Gong and Mao-Ping Song, Dalton Trans., 2011, 40, 5135-5150

Well-defined copper(I) complexes for Click azide–alkyne cycloaddition reactions: one Click beyond, Silvia Díez-González, Catal. Sci. Technol., 2011, 1, 166-178

Access to chiral α-bromo and α-H-substituted tertiary allylic alcohols via copper(I) catalyzed 1,2-addition of Grignard reagents to enones, Ashoka V. R. Madduri, Adriaan J. Minnaard and Syuzanna R. Harutyunyan, Org. Biomol. Chem., 2012, 10, 2878-2884

Catalytic versus stoichiometric dehydrocoupling using main group metals, Robert J. Less, Rebecca L. Melen and Dominic S. Wright, RSC Adv., 2012, 2, 2191-2199

An improved catalyst architecture for rhodium(III) catalyzed C–H activation and its application to pyridone synthesis, Todd K. Hyster and Tomislav Rovis, Chem. Sci., 2011, 2, 1606-1610

Continuous flow organometallic catalysis: new wind in old sails, Ulrich Hintermair, Giancarlo Franciò and Walter Leitner, Chem. Commun., 2011, 47, 3691-3701

Organometallic reactivity: the role of metal–ligand bond energies from a computational perspective, Natalie Fey, Benjamin M. Ridgway, Jesús Jover, Claire L. McMullin and Jeremy N. Harvey, Dalton Trans., 2011, 40, 11184-11191

An introduction to X-ray absorption spectroscopy and its in situ application to organometallic compounds and homogeneous catalysts, Ryan C. Nelson and Jeffrey T. Miller, Catal. Sci. Technol., 2012, 2, 461-470

Palladium-catalyzed cross-coupling reactions of organogold(I) phosphanes with allylic electrophiles, Miguel Peña-López, Miguel Ayán-Varela, Luis A. Sarandeses and José Pérez Sestelo, Org. Biomol. Chem., 2012, 10, 1686-1694

Transition metal complexes with strong absorption of visible light and long-lived triplet excited states: from molecular design to applications, Jianzhang Zhao, Shaomin Ji, Wanhua Wu, Wenting Wu, Huimin Guo, Jifu Sun, Haiyang Sun, Yifan Liu, Qiuting Li and Ling Huang, RSC Adv., 2012, 2, 1712-1728

Mechanism of the gold-catalyzed cyclopropanation of alkenes with 1,6-enynes, Patricia Pérez-Galán, Elena Herrero-Gómez, Daniel T. Hog, Nolwenn J. A. Martin, Feliu Maseras and Antonio M. Echavarren, Chem. Sci., 2011, 2, 141-149

A dual organic/organometallic approach for catalytic ring-opening polymerization, Estefanía Piedra-Arroni, Pierre Brignou, Abderrahmane Amgoune, Sophie M. Guillaume, Jean-François Carpentier and Didier Bourissou, Chem. Commun., 2011, 47, 9828-9830

Half-titanocenes for precise olefin polymerisation: effects of ligand substituents and some mechanistic aspects, Kotohiro Nomura and Jingyu Liu, Dalton Trans., 2011, 40, 7666-7682

Exploring the versatility of a bis(phosphinimine) pincer ligand: effect of sterics on structure and lactide polymerization activity of cationic zinc complexes, Craig A. Wheaton and Paul G. Hayes, Catal. Sci. Technol., 2012, 2, 125-138

Enantioselective Friedel–Crafts alkylation of indole derivatives catalyzed by new Yb(OTf)3-pyridylalkylamine complexes as chiral Lewis acids, Guillaume Grach, Aurelia Dinut, Sylvain Marque, Jérôme Marrot, Richard Gil and Damien Prim, Org. Biomol. Chem., 2011, 9, 497-503

Mononuclear and dinuclear complexes of manganese(III) and Iron(III) supported by 2-salicyloylhydrazono-1,3-dithiane ligand: synthesis, characterization and magnetic properties, Weiwei Zuo, Vitor Rosa, Clarisse Tourbillon, David Specklin, Cheaib Khaled, Mohamedally Kurmoo and Richard Welter, RSC Adv., 2012, 2, 2517-2526

Design and Preparation of New Palladium Precatalysts for C-C and C-N Cross-Coupling Reactions, Nicholas Bruno, Stephen Buchwald and Matthew T Tudge, Chem. Sci., 2012, Accepted Manuscript

Negishi cross-coupling of secondary alkylzinc halides with aryl/heteroaryl halides using Pd–PEPPSI–Ipent, Selçuk Çalimsiz and Michael G. Organ, Chem. Commun., 2011, 47, 5181-5183

Catalytic dehydrogenation of dimethylamine borane by group 4 metallocene alkyne complexes and homoleptic amido compounds, Torsten Beweries, Sven Hansen, Monty Kessler, Marcus Klahn and Uwe Rosenthal, Dalton Trans., 2011, 40, 7689-7692

Bimetallic aluminium(acen) complexes as catalysts for the synthesis of cyclic carbonates from carbon dioxide and epoxides, Michael North and Carl Young, Catal. Sci. Technol., 2011, 1, 93-99

Planar chiral (η5-cyclohexadienyl)- and (η6-arene)-tricarbonylmanganese complexes: synthetic routes and application, Francoise Rose-Munch and Eric Rose, Org. Biomol. Chem., 2011, 9, 4725-4735

Iron-catalysed reduction of carbonyls and olefins, Bryden A. F. Le Bailly and Stephen P. Thomas, RSC Adv., 2011, 1, 1435-1445


Palladium-catalyzed selective oxidative olefination and arylation of 2-pyridones
, Yuye Chen, Fen Wang, Aiqun Jia and Xingwei Li, Chem. Sci., 2012, Advance Article

Hydrogenation of imino bonds with half-sandwich metal catalysts, Chao Wang, Barbara Villa-Marcos and Jianliang Xiao, Chem. Commun., 2011, 47, 9773-9785

Rational design of diphosphorus ligands – a route to superior catalysts, Jason A. Gillespie, Deborah L. Dodds and Paul C. J. Kamer, Dalton Trans., 2010, 39, 2751-2764

For even more articles, take a look at the Dalton Transactions Themed Issue d0 organometallics in catalysis or browse through over 30 RSC Journals covering topics across the chemical sciences.

You can also follow your favourite publications on twitter and sign up to the e-alert service!

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Magnetic mixed-metal molecules

The first Re(IV) system incorporating a 4f ion has been reported by Martínez-Lillo and colleagues at the University of Edinburgh

At present, molecular magnetism in heavy 4d, 5d and 4f-type metal ions is heavily researched since most known systems only involve 3d ions.  Attempts to extend this research into the unexplored area of mixed 5d-4f systems has paid off with this discovery of a mixed Re(IV)-Gd(III) system. 

Magnetic mixed-metal molecules: Rhenium 4f ion mixed with Gadolinium

Single crystals of the new compound, (NBu4)5[Gd{ReBr4(μ-ox)}4(H2O)]·H2O, were analysed at the ESRF to obtain a crystal structure.  Magnetic studies were performed on the new compound, and significant intramolecular antiferromagnetic interactions were found to occur unambiguously between Re(IV) and Gd(III). 

Further work on the preparation of the parent Re(IV)-Ln(III) complex will be carried out in the near future.

To read more about this new compound, its crystal structure and its intramolecular antiferromagnetic coupling, check out this HOT article (free to access for a limited period).

A heteropentanuclear oxalate-bridged [ReIVGdIII] complex: synthesis, crystal structure and magnetic properties

José Martínez-Lillo, Laura Cañadillas-Delgado, Joan Cano,  Francesc Lloret, Miguel Julve and Juan Faus

Posted on behalf of Katie Renouf, Chemical Communications web science writer.

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Highlights from themed issues on ionic liquids

Ionic liquids ChemComm web themed issueCrystal engineering with ionic liquids CrystEngComm CollectionInterfaces of ionic liquids PCCP Themed issue

The field of ionic liquids has seen phenomenal growth in recent years, with the topic spanning a variety of disciplines across the chemical sciences. The recent themed issues from ChemComm, PCCP and CrystEngComm showcase some of the latest developments from a range of scientific subjects utilising the unique properties of ionic liquids.

Highlights from these themed issues include the articles below, which are free to download until the 24th August. You can also access the full themed issues by clicking on the buttons above.

CrystEngComm journal cover imageIonic liquids as crystallisation media for inorganic materials Ejaz Ahmed, Joachim Breternitz, Matthias Friedrich Groh and Michael Ruck, CrystEngComm, 2012, 14, 4874-4885

Ionic liquids in confined geometries Susan Perkin, Phys. Chem. Chem. Phys., 2012, 14, 5052-5062

Fluorescence monitoring of ionic liquid-facilitated biopolymer mobilization and reorganization Luke M. Haverhals, Laura M. Nevin, Matthew P. Foley, E. Kathryn Brown, Hugh C. De Long and Paul C. Trulove, Chem. Commun., 2012, 48, 6417-6419

Hofmeister effects of ionic liquids in protein crystallization: Direct and water-mediated interactions Magdalena Kowacz, Abhik Mukhopadhyay, Ana Luísa Carvalho, José M. S. S. Esperança, Maria J. Romão and Luís Paulo N. Rebelo, CrystEngComm, 2012, 14, 4912-4921

Influence of the ionic liquid/gas surface on ionic liquid chemistry Kevin R. J. Lovelock, Phys. Chem. Chem. Phys., 2012, 14, 5071-5089

ChemComm cover imageOptically responsive switchable ionic liquid for internally-referenced fluorescence monitoring and visual determination of carbon dioxide Shubha Pandey, Sheila N. Baker, Siddharth Pandey and Gary A. Baker, Chem. Commun., 2012, 48, 7043-7045

Supramolecular architectures of symmetrical dicationic ionic liquid based systems Haregewine Tadesse, Alexander J. Blake, Neil R. Champness, John E. Warren, Pierre J. Rizkallah and Peter Licence, CrystEngComm, 2012, 14, 4886-4893

New insights into the interface between a single-crystalline metal electrode and an extremely pure ionic liquid: slow interfacial processes and the influence of temperature on interfacial dynamics Marcel Drüschler, Natalia Borisenko, Jens Wallauer, Christian Winter, Benedikt Huber, Frank Endres and Bernhard Roling, Phys. Chem. Chem. Phys., 2012, 14, 5090-5099

An elegant access to formation and vaporization enthalpies of ionic liquids by indirect DSC experiment and “in silico” calculations Sergey P. Verevkin, Dzmitry H. Zaitsau, Vladimir N. Emel’yanenko, Christoph Schick, Saivenkataraman Jayaraman and Edward J. Maginn, Chem. Commun., 2012, 48, 6915-6917

PCCP journal cover imageIonic liquid-mediated epitaxy of high-quality C60 crystallites in a vacuum Yoko Takeyama, Shingo Maruyama, Hiroki Taniguchi, Mitsuru Itoh, Keiji Ueno and Yuji Matsumoto, CrystEngComm, 2012, 14, 4939-4945

Proton transfer and polarity changes in ionic liquid–water mixtures: a perspective on hydrogen bonds from ab initio molecular dynamics at the example of 1-ethyl-3-methylimidazolium acetate–water mixtures—Part 1 Martin Brehm, Henry Weber, Alfonso S. Pensado, Annegret Stark and Barbara Kirchner, Phys. Chem. Chem. Phys., 2012, 14, 5030-5044

Direct visualization of solution morphology of cellulose in ionic liquids by conventional TEM at room temperature Nan Luo, Yuxia Lv, Dexiu Wang, Jinming Zhang, Jin Wu, Jiasong He and Jun Zhang, Chem. Commun., 2012, 48, 6283-6285

If you’re interested in ionic liquids, why not take a look at the recent cross-journal promotion Incredible ionic liquids: an article collection.

You can keep up to date with all the latest developments across the chemical sciences by signing up to your favourite journal e-alerts or following them on twitter!

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ChemComm’s Impact Factor climbs up once more – 6.169!

Thomson Reuters has just released the 2011 Journal Citation Reports ® and it’s great news for ChemComm.

Our Impact Factor* (IF) has grown once again and now stands at 6.169.

The journal’s success would not be possible without the loyalty of our authors and the commitment of our referees – thank you to all of you who have helped contribute to this impressive figure. And, of course, we sincerely thank our Editorial and Advisory Boards for their continued dedication and commitment.

With an average time of just 55 days from receipt to publication, ChemComm has the fastest average publication times of any chemical journal and with our latest IF as well, it’s clear why ChemComm is the home of urgent, high impact communications from across the chemical sciences.

Join your colleagues today and submit your next high impact communication to ChemComm.

Find out how other RSC journals are ranked in the latest Impact Factor release >

*The IF provides an indication of the average number of citations per paper. Produced annually, IFs are calculated by dividing the number of citations in a year, by the number of citeable articles published in the preceding two years.

 2011 Journal Citation Reports ®, (Thomson Reuters, 2012).

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The Viewpoint: Help us with 100 years of ChemComm history!

This year ChemComm became the first chemistry journal to move to 100 issues per year. To celebrate this achievement, the journal is launching a new article type – the Viewpoint – with the aim of publishing 100 of these very high profile articles over the coming months.

Each of the 100 Viewpoint articles will aim to reflect upon the impact and influence of some of the most renowned papers that ChemComm (or its predecessor journals) have published over the last 100 years but we need help from the community in determining which articles have been the most influential.

Although Chemical Communications was officially launched in 1996, the roots of the journal go much further back through its predecessors – all the way to 1862 with the Journal of the Chemical Society. In the last 100 years, we’ve published close to 100000 articles, with well over 1000 of these articles coming from Nobel laureates alone!

Trying to determine which articles have been the most influential is going to be a massive challenge which will require the help of the entire chemical community – after all, the community is the best judge of what has been truly influential.

We think we’ve managed to come up with some examples of papers that we feel have been significant enough to deserve a Viewpoint:

  1. Hideki Shirakawa, Edwin J. Louis, Chwan K Chiang, Alan J Heeger and Alan G MacDiarmid’s 1977 communication reporting the first electrically conductive polymers.
  2. Neil Bartlett’s publication in 1962 reporting the world’s first noble gas compound, xenon hexafluoroplatinate.
  3. Mathias Brust, Merryl Walker, Donald Bethell, David J. Schiffrin and Robin Whyman’s 1994 communication on the functionalisation of gold nanoparticles with a thiol coating on the surface – ChemComm’s most cited paper of all time!
  4. Geoffrey Wilkinson’s 1965 paper reporting a rhodium catalyst for the hydroformylation of alkenes.

 

Our hope is that the Viewpoint articles will really engage our readers from across the chemical sciences and will shed a personal light on some truly influential chemistry that we have published over the last 10 decades! 

We would love it if you could e-mail us or tweet us (@ChemCommun) your suggestions of which articles (or even small group of seminal articles on one subject) from 1912 onwards, have been key to the development or history of chemistry.

We look forward to hearing from you soon.

History of Chemical Communications 1862 – Present

Journal of the Chemical Society (1862 – 1877)

Journal of the Chemical Society, Transactions (1878 – 1925)

Journal of the Chemical Society (resumed) (1926 – 1965)

Chemical Communications (London) (1965-1968)

Journal of the Chemical Society D: Chemical Communications (1969 – 1971)

Journal of the Chemical Society, Chemical Communications (1972-1995)

Chemical Communications (1996 – Present).

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Chiral Control for the Future?

Tragedies such as the thalidomide scandal led to a re-think as to how pharmaceutical drugs are tested and examined before their sale to the public. Prior to this, racemic mixtures were often administered yet sometimes only one enantiomer of the compound gave the therapeutic properties while the other caused serious side effects. For this reason, huge interest developed in controlling reactions so that only enantiomer would be formed – not a trivial task for the many millions of molecules tumbling around in a round bottom flask! Such is the significance of this problem that the 2001 Nobel Prize for Chemistry was awarded to Sharpless, Noyori and Knowles for work in this field.

Figure 1: Preparation of chiral-at-copper complexes

Many of the methods to obtain this selectivity focus on controlling the orientation of the molecule by building a bulky pocket around the reaction site. Doing so means a reaction can only occur on one side and, as a result, only one enantiomer is created. While this technique has been shown to work well, an alternative approach is to create a reaction site which itself can control the orientation of the molecule. It is exactly this that Paul Newman, Kingsley Cavell and Benson Kariuki at Cardiff University have achieved.

The idea behind the concept is that the reaction site itself is a more efficient way of transferring the control of the chirality. To do this they have created a ‘chiral-at-metal’ Cu(I) complex (Figure 1) which is itself very rare due to the instability of these types of compounds. The characterisation of such an exciting complex is certainly worthy of rapid communication but I hope to see further papers on this work in the near future, giving us an insight into how well this complex performs as a catalyst and how effective it is at transferring chirality. Over time, the catalyst will surely undergo many subtle alterations to improve its performance but only time will tell if this is truly going to be the most effective method of controlling chirality.

Keen to read more? Download this ChemComm article here

Posted on behalf of Ruaraidh McIntosh, Chemical Communications web writer.

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Creating the first high-valent iron oxo phthalocyanines

Phthalocyanines are important industrial oxidation catalysts that are cheap and easy to make but their mechanism remains unclear. Now a team of French and Russian scientists have made and characterised a key intermediate in the catalytic cycle, previously postulated but never obtained.

Pavel Afanasiev and Alexander Sorokin from the CNRS-Université Lyon, France, and colleagues prepared and characterised the first high-valent iron oxo species on the phthalocyanine platform.

They treated tetra-tert-butylphthalocyanine iron chloride with m-chloroperbenzoic acid to give what they later proved to be an Fe(IV) oxo species. Isolation of such a reactive species is extremely challenging so the team characterised the reaction mixture in situ shortly after mixing the reagents. This approach also removed the possibility of the molecule undergoing further transformation en route to the X-ray diffraction facility or NMR spectrometer.

A DFT-optimized structure of the iron-oxo phthalocyanine complex
A DFT-optimized structure of the iron-oxo phthalocyanine complex

The team used at least eight different techniques – including mass spectrometry, UV-vis and EPR spectroscopy, density functional theory (DFT) and X-ray emission studies – in their incredibly thorough examination of the molecule, not only confirm its creation but to fully define many aspects of its electronic structure. These results provide a platform from which a better understanding of iron phthalocyanine catalysts can be developed. 

Keen to read more? Download this ChemComm article here or visit our web collection on Porphyrins & Phthalocyanines. 

Posted on behalf of Ruaraidh McIntosh, Chemical Communications web writer.

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Abstracts invited for International Conference on Physical Organic Chemistry

Good news!

There’s still a chance to submit your oral abstract to ICPOC 21: 21st IUPAC International Conference on Physical Organic Chemistry organised by the Organic Division of the RSC on behalf of IUPAC, to be held 9 – 13 September 2012 at Durham University.

The Scientific Committee is currently reviewing all submissions, and has agreed to accept contributions up to Friday 13 April to allow for the Easter holiday break.

Why join ICPOC 21?

Professor Hiromitsu Maeda, Ritsumeikan University, Japan has won the 2012 ChemComm Emerging Investigator Lectureship and will deliver his lecture at ICPOC 21.

This annual award recognises an emerging scientist in the early stages of their independent academic career. Professor Maeda’s has been particularly commended for his contributions to the fields of organic chemistry, supramolecular chemistry and materials science.

In addition to the outstanding plenary sessions, there will be three parallel sessions over the five days comprising invited lectures and contributed talks, as well as poster sessions.

A broad range of scientists from across the whole community who share a quantitative perspective on chemistry will be there, providing an opportunity to discuss and celebrate the current status, development, and the future of physical organic chemistry.

Make sure you are one of them! Don’t miss the oral abstract submission deadline – 13 April.

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Announcing the ChemComm Emerging Investigators issue 2013

2012 Emerging Investigators issue coverFollowing the amazing successes of the 2011 and 2012 ChemComm Emerging Investigators issues, we are delighted to announce the forthcoming 2013 Emerging Investigators issue. All interested parties should contact the ChemComm Editorial Office in the first instance.

This issue is dedicated to profiling the very best research from scientists in the early stages of their independent careers from across the chemical sciences. We hope to feature principal investigators whose work has the potential to influence future directions in science or result in new and exciting developments.

Also of interest:
ChemComm Emerging Investigators Issue 2012

ChemComm Emerging Investigator Lectureship 2012: The winner is….

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