Archive for July, 2012

Talking inorganic chemistry in Toronto

Growing herbs at the University of Toronto

Growing herbs at the University of Toronto

The conference series International Symposium on Advancing the Chemical Sciences was launched in 2010, to celebrate the launch of the RSC’s new flagship journal, Chemical Science. ISACS8 was the eighth meeting in the series, and the second to have a focus on challenges in inorganic and materials chemistry. This year’s meeting was held at the University of Toronto, Canada.

A slight break in some unusually hot weather meant that for our time in Toronto, we were blessed with perfect weather –  neither too hot nor too cold, but just right! The good weather was clearly being utilised by some members of the university , as was evident in the very healthy looking herbs being growing in the courtyard just outside lecture theatre. I was very good, and did not help myself to any (but I was sorely tempted!).

The conference began on the Thursday evening with an extra special event – a lecture by Profesor Joan Valentine , who was recently awarded an RSC Honorary Fellowship. Her award lecture ‘Manganese and superoxide: Curiosity-driven research at the inorganic chemistry-biology interface’, was a perfect way to open the meeting.

During the  next three days, we covered a diverse range of inorganic and materials topics: main group chemistry, materials for chemistry, magnetism, porous materials and catalysis. The conference featured 16 Plenaries, by Warren Piers, Francois Gabbai, Viola Birss, Sossina Haile, Clare Grey, Simon Aldridge, Joe Hupp, George Christou, Russell Morris, Annie Powell, Noritaka Mizuno, Tom Baker, Kyoko Nozaki, Paul Chirik, Roberta Sessoli and William Dichtel.  The conference programme was completed with a number of contributed talks. As you might expect from ISACS conferences, all the talks were of the highest quality. Snippets of information I learnt from the conference are that Uranium is the Jekyll and Hyde of the Periodic Table, Chemical Science Editors work on Christmas Eve and that we need about 80 of the elements to live our lives.

One of the social highlights of the meeting for me was the speakers’ dinner, held  at the top of the CN Tower. With great food and stunning views, the evening was an excellent way to round off the first full day of the conference.  The conference was a good size ( about 150 delegates) and this  allowed many opportunities to meet new friends and catch up with old ones at the poster sessions, coffee/tea breaks and lunchtimes.  It was good to see a number of people at the conference who I have not seen for a while, including previous Dalton Transactions Development Editor, Anna Roffey, who left the Editorial Office to study for a PhD at UCL, UK over a year ago!

Many thanks to the organisers for arranging a great meeting, in particular local host Doug Stephan and Rachel Thompson from RSC, who in addition to ensuring a well organised meeting, also ensured that we had plenty of sweet treats to keep us going though the day (I have never seen so many cookies…)

Read some articles by the Plenary speakers by following the links below:

Probing the influence of steric bulk on anion binding by triarylboranes: comparative studies of FcB(o-Tol)2, FcB(o-Xyl)2 and FcBMes2, Inke Siewert, Philip Fitzpatrick, Alexander E. J. Broomsgrove, Michael Kelly, Dragoslav Vidovic and Simon Aldridge Dalton Trans., 2011,40, 10345 DOI=10.1039/C1DT10185D

Cyclisation of α,ω-dienes promoted by bis(indenyl)zirconium sandwich and ansa-titanocene dinitrogen complexes, Doris Pun, Donald J. Knobloch, Emil Lobkovsky and Paul J. Chirik Dalton Trans., 2011,40, 7737 DOI=10.1039/C1DT10149H

“Squaring the clusters”: a MnIII4NiII4 molecular square from nickel(II)-induced structural transformation of a MnII/III/IV12 cage Dimitris I. Alexandropoulos, Manolis J. Manos, Constantina Papatriantafyllopoulou, Shreya Mukherjee, Anastasios J. Tasiopoulos, Spyros P. Perlepes, George Christou and Theocharis C. Stamatatos Dalton Trans., 2012,41, 4744 DOI=10.1039/C2DT00030J

Structural and dynamical aspects of alkylammonium salts of a silicodecatungstate as heterogeneous epoxidation catalysts Sayaka Uchida, Keigo Kamata, Yoshiyuki Ogasawara, Megumi Fujita and Noritaka Mizuno Dalton Trans., 2012, Advance Article, DOI=10.1039/C2DT30492A

Metal–organic frameworks for the storage and delivery of biologically active hydrogen sulfide Phoebe K. Allan, Paul S. Wheatley, David Aldous, M. Infas Mohideen, Chiu Tang, Joseph A. Hriljac, Ian L. Megson, Karena W. Chapman, Guy De Weireld, Sebastian Vaesen and Russell E. Morris Dalton Trans., 2012,41, 4060 DOI=10.1039/C2DT12069K

Using the flexible ligand bis(2-hydroxyethyl)amino–tris (hydroxymethyl)methane (“bis–tris”) to access a family of 3d–4f MnIII4Ln4 complexes Amin Khan, Yanhua Lan, George E. Kostakis, Christopher E. Anson and Annie K. Powell Dalton Trans., 2012,41, 8333 DOI=10.1039/C2DT30127J

Magnetic and optical bistability in tetrairon(III) single molecule magnets functionalized with azobenzene groups Thazhe Kootteri Prasad, Giordano Poneti, Lorenzo Sorace, Maria Jesus Rodriguez-Douton, Anne-Laure Barra, Petr Neugebauer, Luca Costantino, Roberta Sessoli and Andrea Cornia Dalton Trans., 2012,41, 8368 DOI=10.1039/C2DT30172E

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Sulfur oxygenation at non-heme iron centers

McQuilken and Goldberg discuss the synthesis, structure and reactivity of non-heme iron(II/III)-thiolate model complexes that are known to react with O2 to give sulfur oxygenates in this hot Perspective.  Comprehension of the pathways involved in sulfur oxygenation will aid research towards catalytic applications involving metal-mediated O2 oxidations as well as developing understanding surrounding nonheme iron enzymes, many of which are vital of important biochemical pathways.

To find out more, read the full Dalton Transactions Perspective now…

Sulfur oxygenation in biomimetic non-heme iron–thiolate complexes
Alison C. McQuilken and David P. Goldberg
Dalton Trans., 2012
DOI: 10.1039/C2DT30806A, Perspective

Are you following us on Twitter? @DaltonTrans

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Hydrazine based hydrogen storage materials

This recent Dalton Transactions cover is by Nikolas Kaltsoyannis and team from UCL and my PhD supervisor, David Antonelli. Doing a PhD in hydrogen storage materials myself, I thought that this would be a good opportunity to blog about some of our group’s research…

The big challenge in hydrogen storage materials research is to develop materials that have a high storage capacity, are fully reversible, and can operate at ambient temperature and pressure. Our group have previously reported chromium hydrazide gels that store hydrogen via the Kubas interaction.  The material has a gravimetric hydrogen storage performance of 3.2 wt% at 298K which corresponds to a volumetric capacity of 40.8 kg H2/m3, meeting the US Department of Energy’s 2015 target for volumetric density (40 kg/m3).

In this latest Dalton Transactions article, the Cr(II) binding sites were studied computationally to further study the interaction with H2. Strong evidence suggests that the metal-H2 interaction is Kubas type (confirming our previously reported results) – the Kubas interaction between a transition metal and H2 involves σ-donation from the filled H‑H σ-bonding orbital into an empty transition metal d orbital, and is strengthened by back-donation from a filled metal d orbital into the vacant σ*  orbital of the H2 molecule. The binding model is similar to the Dewar-Chatt-Duncanson model for the bonding of CO ligands to transition metals.

Kaltsoyannis and team extended the system to incorporate other transition metal binding sites: Ti(II), V(II) and Mn(II). They found that H2 did not bind to Mn(II) suggesting that Mn(II) materials may not perform well for hydrogen storage. Hydrogen did bind to V(II) and Ti(II) and calculations indicate 5 and 7 wt% gravimetric storage respectively, surpassing the DOE’s goal for gravimetric storage.

This paper shows that materials based on V(II) and Ti(II) could potentially perform better than the experimentally-realised chromium hydrazide gels.

To find out more, read the full Dalton Transactions article now…

The Kubas interaction in M(II)  (M = Ti, V, Cr) hydrazine-based hydrogen storage materials: a DFT study
Claire V. J. Skipper, Ahmad Hamaed, David M. Antonelli and Nikolas Kaltsoyannis

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Frustrated Lewis pairs themed issue now published

We strongly recommend you have a browse of Dalton Transactions’ latest themed issue in Frustrated Lewis Pairs.

As Guest Editor, Doug Stephan says in his Editorial: there’s nothing frustrating about frustrated Lewis pairs! Particularly as these highly reactive compounds are gaining increasing attention from researchers wishing to activate dihydrogen, olefins, disulfides, CO2… the list continues…

The issue contains 18 articles dedicated to the topic – a small selection is below:

Hydrogen activation by 2-boryl-N,N-dialkylanilines: a revision of Piers’ ansa-aminoborane
Konstantin Chernichenko, Martin Nieger, Markku Leskelä and Timo Repo

Frustrated Lewis pair addition to conjugated diynes: Formation of zwitterionic 1,2,3-butatriene derivatives
Philipp Feldhaus, Birgitta Schirmer, Birgit Wibbeling, Constantin G. Daniliuc, Roland Fröhlich, Stefan Grimme, Gerald Kehr and Gerhard Erker

Fixation of carbon dioxide and related small molecules by a bifunctional frustrated pyrazolylborane Lewis pair
Eileen Theuergarten, Janin Schlösser, Danny Schlüns, Matthias Freytag, Constantin G. Daniliuc, Peter G. Jones and Matthias Tamm

Access the issue here

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Winners at the X Congresso del Gruppo Interdivisionale di Chimica Organometallica

Blerina Gjoka (left) and Daniela Intrieri (right) after winning their Dalton Transactions Poster Prizes at the X Co.G.I.C.O

Blerina Gjoka (left) and Daniela Intrieri (right) after winning their Dalton Transactions Poster Prizes at the X Co.G.I.C.O

The Congresso del Gruppo Interdivisionale di Chimica Organometallica della Societa’ Chimica Italiana (Co.G.I.C.O) recently held their 10th meeting in the beautiful city of Padua, in the North of Italy. Founded in 1991, the group meets every 2 years to discuss recent developments in the field of organometallic chemistry

Attracting established international scientists and young researchers alike, this year the delegates enjoyed a range of talks from the plenary speakers: 

Paul J. Dyson, Lausanne, “Organoruthenium agents for the treatment of invasive tumours” 

Steven P. Nolan, St Andrews, “Recent advances in late transition metal-NHC mediated catalysis” 

Kay Severin, Lausanne, “Chemistry with organometallic half-sandwich complexes: sensors, nanostructures, and catalysts” 

Christophe Coperet, Zurich, “Control functionalization of surfaces towards single-site catalysts” 

Poster sessions were also held during the meeting and we are delighted to announce that the winners of the two Dalton Transactions Poster Prize’s were Daniela Intrieri of Università degli Studi di Milano, and Blerina Gjoka of Università degli studi di Padova. 

Daniela’s poster was on the topic of ‘Ru(TPP)CO-Catalysed 2-Azido Biaryls Annulation to Afford Phenanthridine and Dihydrophenanthridine Derivatives’, and Blerina’s on ‘Iron(III) Amino Triphenolate Complexes as Catalysts for CO2 Fixation’

See the conference homepage for more details

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Ambient hydrogen activation by frustrated aminoboranes

Almost ten years ago, Piers et al. described how frustrated aminoboranes could be used to activate molecular hydrogen by exploiting their frustrated Lewis pairs.  Unfortunately the ansa-aminoborane they investigated proved incapable of activating H2, and so this contribution was very much overlooked in the ongoing search for facile H2 activation.

ansa-aminoborane 3A frustrated Lewis pair, in this case, is a molecule that contains a Lewis acid group and a Lewis base group kept apart due to sterics.  Such compounds are, perhaps unsurprisingly, very reactive.  The most important practical application of FLPs is most likely to be the catalysed hydrogenation of polar double bonds under ambient conditions.

The Repo group at the University of Helsinki describe how they have overcome the problems encountered in 2003 to produce two new ansa-aminoboranes which are both capable of activating molecular hydrogen under ambient conditions.  One of their new compounds even shows selective reversible H2 activation at room temperature, providing exciting new developments for FLP catalysis.

Read more about these new catalysts, including why they outperform their predecessors, in this HOT article.

Hydrogen activation by 2-boryl-N,N-dialkylanilines: a revision of Piers’ ansa-aminoborane
Konstantin Chernichenko, Martin Nieger, Markku Leskelä and Timo Repo

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Highlights from themed issues covering metal–organic frameworks

MOF's Metal organic frameworks coordination polymers

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The exciting chemistry of metal-organic frameworks (MOF’s) attracts interest from a range of communities within the chemical sciences. Recently  the Journal of Materials Chemistry published a themed issue ‘Integrating functionality into metal–organic frameworks’ and Dalton Transactions ‘Coordination chemistry in the solid state’.

You can see the full issues by clicking on the links above, alternatively you can browse the highlights below, which are free to download until the 27th July.

Metal–organic frameworks as scaffolds for the encapsulation of active species: state of the art and future perspectives
Jana Juan-Alcañiz, Jorge Gascon and Freek Kapteijn
J. Mater. Chem., 2012,22, 10102-10118
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Supramolecular isomers of metal–organic frameworks: the role of a new mixed donor imidazolate-carboxylate tetradentate ligand
Victoria J. Richards, Stephen P. Argent, Adam Kewley, Alexander J. Blake, William Lewis and Neil R. Champness
Dalton Trans., 2012, 41, 4020-4026

Effect of the organic functionalization of flexible MOFs on the adsorption of CO2
Thomas Devic, Fabrice Salles, Sandrine Bourrelly, Béatrice Moulin, Guillaume Maurin, Patricia Horcajada, Christian Serre, Alexandre Vimont, Jean-Claude Lavalley, Hervé Leclerc, Guillaume Clet, Marco Daturi, Phillip L. Llewellyn, Yaroslav Filinchuk and Gérard Férey
J. Mater. Chem., 2012, 22, 10266-10273

Highly oriented surface-growth and covalent dye labeling of mesoporous metal–organic frameworks
Florian M. Hinterholzinger, Stefan Wuttke, Pascal Roy, Thomas Preuße, Andreas Schaate, Peter Behrens, Adelheid Godt and Thomas Bein
Dalton Trans., 2012, 41, 3899-3901

Structural flexibility and intrinsic dynamics in the M2(2,6-ndc)2(dabco) (M = Ni, Cu, Co, Zn) metal–organic frameworks
Nicole Klein, Herbert C. Hoffmann, Amandine Cadiau, Juergen Getzschmann, Martin R. Lohe, Silvia Paasch, Thomas Heydenreich, Karim Adil, Irena Senkovska, Eike Brunner and Stefan Kaskel
J. Mater. Chem., 2012, 22, 10303-1031

MOF's Metal organic frameworks coordination polymersHydrogen adsorption in the metal–organic frameworks Fe2(dobdc) and Fe2(O2)(dobdc)
Wendy L. Queen, Eric D. Bloch, Craig M. Brown, Matthew R. Hudson, Jarad A. Mason, Leslie J. Murray, Anibal Javier Ramirez-Cuesta, Vanessa K. Peterson and Jeffrey R. Long
Dalton Trans., 2012, 41, 4180-4187

You might also be interested in the recent CrystEngComm Highlight

Coordination polymers, metal–organic frameworks and the need for terminology guidelines
Stuart R. Batten, Neil R. Champness, Xiao-Ming Chen, Javier Garcia-Martinez, Susumu Kitagawa, Lars Öhrström, Michael O’Keeffe, Myunghyun Paik Suh and Jan Reedijk
CrystEngComm, 2012, 14, 3001-3004

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Articles from around the world: Korea

This month we are highlighting some of the excellent articles published in Dalton Transactions from South Korea.

Click on the links below to download the articles…

A double-walled triangular metal-organic macrocycle based on a [Cu2(COO)4] square paddle-wheel secondary building unit
Xiaokai Song, Xinfang Liu, Minhak Oh and Myoung Soo Lah
Dalton. Trans., 2010, 39, 6178–6180

Preparation and characterisation of divalent hard and soft metal (M = Ca, Co, Cu, Zn, Cd, Hg and Pb) complexes of 1,10-dithia-18-crown-6: structural versatility
In-Hyeok Park, Ki-Min Park and Shim Sung Lee
Dalton Trans., 2010, 39, 9696–9704

Self-assembled molecular squares containing metal-based donor: synthesis and application in the sensing of nitro-aromatics
Vaishali Vajpayee, Hyunuk Kim, Anurag Mishra, Partha Sarathi Mukherjee, Peter J. Stang, Min Hyung Lee, Hwan Kyu Kim and Ki-Whan Chi
Dalton Trans., 2011,40, 3112–3115

Two-dimensional metal–organic frameworks with blue luminescence
Seong Huh, Suhyun Jung, Youngmee Kim, Sung-Jin Kim and Seongsoon Park
Dalton Trans., 2010, 39, 1261–1265

Canted antiferromagnetism and spin reorientation transition in layered inorganic–organic perovskite (C6H5CH2CH2NH3)2MnCl4
Seong-Hun Park, In-Hwan Oh, Sungil Park, Younbong Park, Ji Hyun Kim and Young-Duk Huh
Dalton Trans., 2012, 41, 1237–1242

Self-assembled metalla-bowls for selective sensing of multi-carboxylate anions
Anurag Mishra, Vaishali Vajpayee, Hyunuk Kim, Min Hyung Lee, Hyunji Jung, Ming Wang, Peter J. Stang and Ki-Whan Chi
Dalton Trans., 2012, 41, 1195–1201

Anion variation on a cobalt(III) complex of salen-type ligand tethered by four quaternary ammonium salts for CO2/epoxide copolymerization
Jina Yoo, Sung Jae Na, Hyeong Cheol Park, Anish Cyriac and Bun Yeoul Lee
Dalton Trans., 2010, 39, 2622–2630

Why not check out last year’s New Talent: Asia themed issue for more articles from Korea and beyond?

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Register now for Dalton Discussion 13

There’s still just time to submit a poster for Inorganic Photophysics and Photochemistry – Fundamentals and Applications: Dalton Discussion 13. The deadline date is 6 July.

The fields of photophysics and photochemistry of metal complexes – and their associated spectroscopic methodology – have never been more topical. This Discussion will bring together people from a wide range of disciplines, from theory and ultrafast spectroscopy to medicinal chemistry and biology, but all with a shared interest in the use of light.

Registration is quick and simple via our online booking system, so act today and benefit from early bird savings.

Taking part in this Dalton Discussion is a great way to get your own research work better known. You can also have your own poster abstract space at the meeting – submit yours now.

I will be attending the Discussion and would love to meet you, so come and join this timely and thought-provoking discussion and hear speakers who are among the key scientists in the field. Contributions from all photophysics-based disciplines will be welcome.

Also of interest: The RSC’s policy report on Solar Fuels and Artificial Photosynthesis: Science and innovation to change our future energy options

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Dalton Transactions Board members awarded RSC prizes

The RSC has recently announced the recipients of the RSC 2012 Awards. These prestigious awards recognise the outstanding work of scientists working in all branches of the chemical sciences.

Dalton Transactions Editorial Board Chair, Philip Mountford was awarded with the Frankland Award for “his seminal work on metal-ligand multiple bonding of the early transition elements and applications to the design of new polymerisation catalysts and to novel chemistry of main group and lanthanide compounds.”

Dalton Transactions Editorial Board member, Polly Arnold, received one of the Corday-Morgan Prizes for her “outstanding contributions to the application of organometallic uranium chemistry to small molecule activation.”

Whilst the Ludwig Mond Award was given to Dalton Transactions Advisory Board member and Chem Soc Rev Associate Editor, Douglas Stephan.

For details on other prize winners, visit the RSC website.

From the Dalton Transactions Editorial Office, a big well done to Philip, Polly and Doug!

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