Archive for the ‘Inorganic’ Category

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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pHantastic developments in lysosomal storage disease research

Lysosomes are cellular organelles that contain enzymes which break down cellular waste, a bit like stomachs. They have an internal pH of 4.8 and maintain this acidic pH (compared to the cytosol, pH 7.2) by pumping protons across the membrane. Changes in lysosomal pH can indicate the onset of disease.  In fact, elevated lysosomal pH has been noted in several lysosomal storage diseases. This group of around 50 rare, inherited, metabolic disorders result in symptoms such as seizures, deafness and/or blindness.

Now David Parker and colleagues at the University of Durham have designed responsive, low molecular weight probes which can permeate the target organelle and report the pH using a ratiometric signal. The probes could help evaluate the impact of drugs created to treat lysosomal storage diseases.

The team made europium and terbium complexes of two structurally related ligands that contain a sulfonamide moiety which acts like a switch, reversibly binding to the lanthanide and changing the metal coordination environment. The change is signalled by variation of emission spectral form and relative intensity and also modulates the circular polarisation of luminescence as the local helicity at the metal centre switches.  

Testing in a range of cell lines and altering the pH of the cellular and intracellular environment, the researchers developed an emission intensity ratio method using lanthanide luminescence which can be used to assess lysosomal pH variation for the first time.

Find out more by reading their ChemComm communication, free to download for a limited period.

Also of interest:
Times have changed since David Parker wrote his first ChemComm on a typewriter. He discusses his research path, chemical prostitution and targeted devastation in his ChemComm interview.

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Silica sheets to deliver DNA into cells for disease prevention and treatment

Scientists in Japan have made a new DNA delivery substrate based on networks of bio-friendly upright silica sheets. The network of sheets forms a porous film on to which they can immobilise DNA, ready for delivery (transfection) into cells. The transfection efficiency of the silica film is approximately double that of solution-based transfection. Gene transfection is a potential method for preventing and treating diseases and analysing cell functions.

 

Silica sheets to deliver DNA into cells for disease prevention and treatment

Link to journal article
Silica-based Gene Reverse Transfection: Upright Nanosheet Network for Promoted DNA Delivery to Cell

Q Ji et al

Chem. Commun., 2012, DOI: 10.1039/c2cc34289h

 

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Easy synthesis of nanocups and nanopatches

Graphical abstract: Facile synthesis of functional Au nanopatches and nanocupsA gold nanocup – it sounds like something a posh fairy might drink out of. But actually, metal nanocups are promising particles for sensing and nanoelectronics thanks to their plasmon coupling and light scattering properties. Until now, they have been difficult to make but Jinlong Gong at Tianjin University, China, Zhihong Nie, at the University of Maryland, USA, and colleagues have developed a new easy route suitable for large scale synthesis.

The team used a template-free, liquid-liquid interfacial reaction to build up the gold cups round polymer particles. These so called ‘patchy particles’ are themselves attractive as building blocks for nanostructures due to the directional interactions between the metal patches. Removing the polymers using organic solvent revealed the nanocups with diameters as small as 76 nm. The team demonstrated that the cups can enhance surface enhanced Raman scattering intensity up to the order of 108.

Find out more – download Gong’s ChemComm communication

Want to learn more about surface enhanced Raman spectroscopy? Check out the ChemComm web theme >

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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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REMINDER: ChemComm-RSC Prizes and Awards Symposium in Oxford on Wednesday

Don’t miss out on Wednesday’s ChemComm–RSC Prizes & Awards Symposium jointly organised with the RSC Dalton Division!

Date: Wednesday 23rd May 2012
Location: Inorganic Chemistry Laboratory lecture theatre, South Parks Road, University of Oxford, UK
Time: 11am – 6.45 pm

The purpose of this event is to bring together scientists in a stimulating and friendly environment to recognise the achievements of individuals in advancing the chemical sciences and also to foster collaborations. The symposium will appeal to academic and industrial scientists with an interest in inorganic and supramolecular chemistry. Attendance at the symposium is FREE OF CHARGE and student participation is strongly encouraged.

The following distinguished scientists have agreed to speak:

To register for the symposium, please complete the online registration form.

ChemComm-RSC Prizes and Awards Symposium programme

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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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Free ChemComm inorganic and supramolecular content

The ChemComm–RSC Prizes & Awards Symposium jointly organised with the Dalton Division takes place at the University of Oxford on 23rd May with the theme of inorganic and supramolecular chemistry.

This is ChemComm’s second UK-based symposium and to celebrate we’ve made some of our best content free to access for a limited period.

We hope you enjoy these articles – but don’t delay! Free access only runs until 30th May.

Germanium/phosphorus cage compounds with germanium in three different oxidation states
Stefan Almstätter, Gábor Balázs, Michael Bodensteiner and Manfred Scheer
Chem. Commun., 2011, 47, 9998-10000
DOI: 10.1039/C1CC13937A

Selective gas sorption in a [2+3] ‘propeller’ cage crystal
Shan Jiang, John Bacsa, Xiaofeng Wu, James T. A. Jones, Robert Dawson, Abbie Trewin, Dave J. Adams and Andrew I. Cooper
Chem. Commun., 2011, 47, 8919-8921
DOI: 10.1039/C1CC12460A

Reversible anion-templated self-assembly of [2+2] and [3+3] metallomacrocycles containing a new dicopper(I) motif
Emily F. V. Dry, Jack K. Clegg, Boris Breiner, Daniel E. Whitaker, Roman Stefak and Jonathan R. Nitschke
Chem. Commun., 2011, 47, 6021-6023
DOI: 10.1039/C1CC11206F

Cleavage of dinitrogen to yield a (t-BuPOCOP)molybdenum(IV) nitride
Travis J. Hebden, Richard R. Schrock, Michael K. Takase and Peter Müller
Chem. Commun., 2012, 48, 1851-1853
DOI: 10.1039/C2CC17634C

Metal-free diastereoselective catalytic hydrogenations of imines using B(C6F5)3
Zachariah M. Heiden and Douglas W. Stephan
Chem. Commun., 2011, 47, 5729-5731
DOI: 10.1039/C1CC10438A

Activation of phosphorus by group 14 elements in low oxidation states
Shabana Khan, Sakya S. Sen and Herbert W. Roesky
Chem. Commun., 2012, 48, 2169-2179
DOI: 10.1039/C2CC17449A

Twisted molecular magnets
Ross Inglis, Constantinos J. Milios, Leigh F. Jones, Stergios Piligkos and Euan K. Brechin
Chem. Commun., 2012, 48, 181-190
DOI: 10.1039/C1CC13558A

Luminescent metal complexes of d6, d8 and d10 transition metal centres
Vivian Wing-Wah Yam and Keith Man-Chung Wong
Chem. Commun., 2011, 47, 11579-11592
DOI: 10.1039/C1CC13767K

Uranium-mediated activation of small molecules
Polly L. Arnold
Chem. Commun., 2011, 47, 9005-9010
DOI: 10.1039/C1CC10834D

Also of interest: Take at look at our web themes on Supramolecular Chemistry and Frontiers in Molecular Main Group Chemistry.

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Sustainable Inorganic Chemistry – free content for a limited period

Sustainable Inorganic Chemistry Symposium

ChemComm is delighted to be sponsoring the forthcoming Symposium on Sustainable Inorganic Chemistry  along with the ACS Division of Inorganic Chemistry. The symposium will take place at the ACS Spring 2012 National Meeting & Exposition in San Diego starting on 25th March.

To celebrate we’ve made some articles published by the symposium speakers free to access for a limited period.

We hope you enjoy these articles – but don’t delay! Free access only runs until 1st April

Selective liquid phase oxidation with supported metal nanoparticles
Nikolaos Dimitratos, Jose A. Lopez-Sanchez and Graham J. Hutchings
Chem. Sci., 2012, 3, 20-44

Mesoscopic organic nanosheets peeled from stacked 2D covalent frameworks
Yugen Zhang, Meixuan Tan, Hai Li, Yuangang Zheng, Shujun Gao, Hua Zhang and Jackie Y. Ying
Chem. Commun., 2011, 47, 7365-7367

Self-assembly in the electrical double layer of ionic liquids
Susan Perkin, Lorna Crowhurst, Heiko Niedermeyer, Tom Welton, Alexander M. Smith and Nitya Nand Gosvami
Chem. Commun., 2011, 47, 6572-6574

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

CO2 selectivity of a 1D microporous adenine-based metal–organic framework synthesised in water
Kyriakos C. Stylianou, John E. Warren, Samantha Y. Chong, Jeremy Rabone, John Bacsa, Darren Bradshaw and Matthew J. Rosseinsky
Chem. Commun., 2011, 47, 3389-3391

Room temperature oxidation of methyl orange and methanol over Pt–HCa2Nb3O10 and Pt–WO3 catalysts without light
Emiliana Dvininov, Upendra A. Joshi, James R. Darwent, John B. Claridge, Zhongling Xu and Matthew J. Rosseinsky
Chem. Commun., 2011, 47, 881-883

Tunable, light-assisted co-generation of CO and H2 from CO2 and H2O by Re(bipy-tbu)(CO)3Cl and p-Si in non-aqueous medium
Bhupendra Kumar, Jonathan M. Smieja, Alissa F. Sasayama and Clifford P. Kubiak
Chem. Commun., 2012, 48, 272-274

Photocatalytic H2 evolution from neutral water with a molecular cobalt catalyst on a dye-sensitised TiO2 nanoparticle
Fezile Lakadamyali and Erwin Reisner
Chem. Commun., 2011, 47, 1695-1697

Transition metal catalysed ammonia-borane dehydrogenation in ionic liquids
William R. H. Wright, Emily R. Berkeley, L. R. Alden, R. Tom Baker and Larry G. Sneddon
Chem. Commun., 2011, 47, 3177-3179

Co and Mn polysiloxanes as unique initiator–catalyst-systems for the selective liquid phase oxidation of o-xylene
Tobias Förster, Stephan A. Schunk, Andreas Jentys and Johannes A. Lercher
Chem. Commun., 2011, 47, 3254-3256

@ChemCommun               Follow the symposium at #CCsymp

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Sustainable Inorganic Chemistry Symposium at Spring ACS Meeting

Sustainable Inorganic Chemistry Symposium

We are delighted to announce the forthcoming Symposium on Sustainable Inorganic Chemistry sponsored by ChemComm and the ACS Division of Inorganic Chemistry, which will be held at the ACS Spring 2012 National Meeting & Exposition.

Date: 25-27 March 2012
Location: San Diego Convention Center – Room 9, San Diego, USA

With 22 invited talks across three days by both world-leading authorities and incredibly talented emerging researchers, the symposium will cover CO2 capture and recycle; energy storage; photovoltaics; water purification; unconventional resources; and energy efficiency, all of which are underpinned by inorganic chemistry.

View the schedule >

ChemComm Editor Robert Eagling is co-organiser of the symposium – let him know if you plan to attend.

Twitter Bird@ChemCommun               Follow the symposium at #CCsymp

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