A Novel Decanuclear Cobalt(II) Cluster

Polynuclear complexes contain several metal atoms or ions in a single coordination species and therefore their electronic structures and magnetic properties can be quite complex. These properties give polynuclear complexes potential for applications in information storage devices and molecular magnets. 

decanuclear Co(II) cluster with adamantane-like metallic skeleton

Ruren Xu, Jihong Yu and their  team at Jilin University, China have reported the synthesis of a novel cobalt(II) polynuclear complex. This new complex is a decanuclear cobalt (II) cluster with bridging Co32- anions  and 8-hydroxyquinoline ligands. Interestingly, the ten cobalts are arranged in an adamantane topology which is a chair-like conformation, The adamantane topology of the cobalt culster can be seen clearly in green in the left hand figure. To the researchers’ knowledge, this is the first example of a metallic skeleton with an adamantane topology in a polynuclear complex. It was also found that an antiferromagentic interaction exists within the complex.

This novel complex is unlike any other cobalt polynuclear complex that has been reported before.

To find out more about the fascinating stucture of this decanuclear cobalt (II) cluster, read the full Dalton Transactions article:

A novel decanuclear Co(II) cluster with adamantane-like metallic skeleton supported by 8-hydroxyquinoline and in situ formed CO32− anions
Lei Wang, Yi Li, Yu Peng, Zhiqiang Liang, Jihong Yu and Ruren Xu

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Boranes and Borohydrides themed issue – submissions open

Boranes and Borohydrides themed issueSubmissions are now open for the Dalton Transactions themed issue on Boranes and Borohydrides, guest edited by Professor Simon Aldridge (University of Oxford).

Borane and borohydride containing molecules/materials constitute an exciting and rapidly developing field which spans a wide breadth of chemistry, and has seen a number of major fundamental developments in recent years. Applications in fields as diverse as catalysis, organic synthesis, polymer chemistry and functional materials science, sensors, and energy highlight the impact of research currently being carried out.

This Dalton Transactions themed issue will seek to highlight to the inorganic research community the latest and very best research in the field.

We will consider all types of article: Communications, Full Papers, Frontiers and Perspectives (please contact the Editorial Office if you would like to contribute a Frontier or Perspective article). For further information on article types, see our author guidelines. Please note that the normal refereeing procedure will apply and inclusion in the issue is subject to the discretion of the guest editor.

Submission deadline: 20th July 2012

Submit now! We look forward to receiving it shortly…

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Computational investigation suggests symbiotic interaction between borane-phosphine frustrated Lewis pairs and nitrous oxide

Computational studies of complexation of nitrous oxide by borane–phosphine frustrated Lewis pairsThomas Gilbert from Northern Illinois University reports on a computational study looking at Ar3B–ONN–PR3 complexes that result from reactions between borane-phosphine frustrated Lewis pairs and N2O.  By exploring the structure, stability, mechanism of formation and functionalisation of Ar3B–ONN–PR3 complexes, we can further understand how frustrated Lewis pairs can capture small molecules, like N2O, and hold them for derivatisation, in a similar way to enzymes.

A key finding from this study is a symbiotic relationship that forms between Lewis acid and Lewis base to overcome endothermic or weakly exothermic energetics, forming one structural isomer in preference to others.  Gilbert makes several other exciting conclusions so download the manuscript whilst it’s free to find out more….

Computational studies of complexation of nitrous oxide by borane–phosphine frustrated Lewis pairs
Thomas M. Gilbert
Dalton Trans., 2012
DOI: 10.1039/C2DT30208J

Frustrated Lewis pairs are compounds or mixtures combining sterically hindered Lewis donors and acceptors.  Such systems are capable of unique reactivity with fascinating applications in stoichiometry and catalysis.  Dalton Transactions will be publishing a themed issue on frustrated Lewis pairs later in the year – below are some other articles due to be included in the issue:

Exchange chemistry of tBu3P(CO2)B(C6F5)2Cl
Rebecca C. Neu,  Gabriel Ménard and Douglas W. Stephan
Dalton Trans., 2012
DOI: 10.1039/C2DT30206C

Dimeric aluminum–phosphorus compounds as masked frustrated Lewis pairs for small molecule activation
Steffi Roters,  Christian Appelt,  Hauke Westenberg,  Alexander Hepp,  J. Chris Slootweg,  Koop Lammertsma and Werner Uhl
Dalton Trans., 2012
DOI: 10.1039/C2DT30080J

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Bimetallic tuneable MOFs – a one-pot wonder

Laurance Beauvais and colleagues have synthesised a mixed metal MOF allowing different divalent metal ions to be easily incorporated into the framework. A bimetallic approach means that one metal can be used for structural integrity, whilst the other can be functional, for application in catalysis for example. The team chose a porprhyrin-based ligand to underpin the framework since this has two distinct metal binding sites – a structural metal binding site at the carboxy and pyridyl ligands; and a functional metal binding site within the porphyrin cavity.

mixed metal porphyrin

By adding the metals together in a one-pot reaction, the porphyrin framework incorporates both metals with the larger metal ions occupying the structural sites.

With the synthetic method now done and dusted, the team will now look into the catalytic and luminescent properties of these coordination framework materials.

Read Beauvais’ HOT article now… A heterometallic metal-organic framework with tuneable reactive metal sites: synthesis, characterization, and reactivity
Nathan C. Smythe, Derek P. Butler, Curtis E. Moore, William R. McGowan, Arnold L. Rheingold and Laurance G. Beauvais

Are you following us on Twitter? @DaltonTrans

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Fixing Nitrogen

The well known Haber Bosch process converts nitrogen and hydrogen into ammonia under very harsh reaction conditions. Nitrogen fixation in biology however, takes place at ambient pressure and temperature. A long term goal of researchers has been to achieve nitrogen fixation under ambient conditions.

Whilst molybdenum- and tungsten-dinitrogen complexes containing phosphine ligands are able to reduce nitrogen to ammonia under ambient conditions (in the presence of an acid such as sulfuric acid), these complexes are unable to produce ammonia from molecular dihydrogen.

Yoshiaki Nishibayashi from the University of Tokyo has recently developed a dinitrogen-bridged dimolybdenum complex bearing tridentate PNP pincer ligand which is a diphosphine containing a nitrogen linker. The catalyst is able to produce 23 equivalents of ammonia under atmospheric pressure. A second molybdenum based catalyst, this time bearing ferrocenyl diphosphine ligands is able to produce 226 equivalents of silylamine in the presence of trimethylsilyl chloride and sodium under atmospheric pressure. A future study of the reaction mechanism of these new catalytic systems could provide more insight to guide the design of more effective catalyzed nitrogen fixation in the future.

Nishibayashi has written a comprehensive article that discusses previous work on catalysts for dinitrogen fixation and also reports his recent work on two new nitrogen fixation systems catalyzed by molybdenum-dintrogen complexes. To find out more read the Dalton Transactions Perspective article.

Yoshiaki Nishibayashi
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT30105A
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HOT Article: Role of Zn and Mn in Parkinson’s Disease

Model of the YPK9 proteinIn this HOT article, Zoroddu and coworkers present NMR (mono- and bi-dimensional) and EPR analysis of Zn and Mn complexation to small fragments of the Park9 gene  (a member of the P5-type ATPase family) important in Parkinson’s disease (PD).   This type of study may provide an insight into the understanding of the connection between genetic and environmental PD causes.  The group are planning further investigations, involving the role of the entire protein.

Read more for FREE until 16th April 2012 at:

Mn(II) and Zn(II) interactions with peptide fragments from Parkinson’s disease genes
Serenella Medici,  Massimiliano Peana,  Lucia Gemma Delogu and Maria Antonietta Zoroddu
Dalton Trans., 2012, 41, 4378-4388
DOI: 10.1039/C2DT12168A

The following critical review may also be of interest:

The potential application of iron chelators for the treatment of neurodegenerative diseases
Robert C. Hider,  Sourav Roy,  Yong Min Ma,  Xiao Le Kong and Jane Preston
Metallomics, 2011, 3, 239-249
DOI: 10.1039/C0MT00087F

You can also keep up to date with the latest news in inorganic chemistry by following us on twitter or signing up to our e-alert service.

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Exchanging ligands on semiconducting nanocrystals

Semiconductors are at the heart of nearly all things computerised, and with nearly all things computerised that makes semiconductors important. Semiconducting nanocrystals have become an interesting area of research because as colloidal inks they can potentially be used to easily print onto substrates to create photo-voltaic devices or a broad range of electronic devices.

CdSe nanocrystals undergoing ligand exchange and thermolysis

CdSe nanocrystals undergoing ligand exchange and thermolysis

This Hot Communication from the Brutchey group details the use of a ligand which exchanges with the capping ligand of semiconducting CdSe nanocrystals making them highly dispersible in a range of polar solvents (in DMF a stable colloid forms for > 2 weeks). Under mild conditions thermolysis transforms the surface bound ligands to thiocyanate in situ, producing nanocrystal films of CdSe(SCN). There are also indications of improved inter-particle coupling…

Nanocrystal ligand exchange with 1,2,3,4-thiatriazole-5-thiolate and its facile in situ conversion to thiocyanate
David H. Webber and Richard L. Brutchey

This Hot Article is part of our up-coming themed issue ‘New Talent Americas’, Guest Edited by Dan Mindiola and John Arnold, other articles due to be published in this special issue include:

Perceiving Molecular Themes in the Structures and Bonding of Intermetallic Phases: The Role of Hückel Theory in an Ab Initio Era
Timothy E. Stacey and Daniel Fredrickson

Splitting water with rust: hematite photoelectrochemistry
Thomas W. Hamann

A heterobimetallic metal–organic framework with tunable reactive metal sites: synthesis, characterization, and reactivity
Nathan C. Smythe, Derek P. Butler, Curtis E. Moore, William R. McGowan, Arnold L. Rheingold and Laurance G. Beauvais

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Nanocatalyst for hydrogen release

hydrogen release from the dimethlyamine-borane complexAmine borane complexes are a promising solution for storing hydrogen, particularly as we move towards a hydrogen economy. Whilst focusing on developing the dehydrogenation of such complexes (namely dimethylamine-borane), scientists from Turkey have shown that you need to think small to think big by preparing a nanoparticle catalyst for the reaction.

By adding ruthenium (III) chloride to the hydrogen storing dimethlyamine-borane complex, the team found that ruthenium nanoparticles are generated in-situ which further work to catalyse the release of hydrogen from the complex.

Nanosizing the catalyst means a higher proportion of surface atoms are available for the hydrogen-storage complex – the result is greater catalytic activity and faster hydrogen generation.

Read the HOT article now for free… Hydrogen liberation from the hydrolytic dehydrogenation of dimethylamine–borane at room temperature by using a novel ruthenium nanocatalyst
Salim Caliskan, Mehmet Zahmakiran, Feyyaz Durap and Saim Özkar

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Top ten most accessed articles in February

This month sees the following articles in Dalton Transactions that are in the top ten most accessed:-

The end of iodide? Cobalt complex redox shuttles in DSSCs 
Thomas W. Hamann  
Dalton Trans., 2012, 41, 3111-3115 DOI: 10.1039/C2DT12362B  
   
Enhanced cytotoxicity of silver complexes bearing bidentate N-heterocyclic carbene ligands 
Diana C. F. Monteiro ,  Roger M. Phillips ,  Benjamin D. Crossley ,  Jake Fielden and Charlotte E. Willans  
Dalton Trans., 2012, 41, 3720-3725 DOI: 10.1039/C2DT12399A  
   

A series of isostructural mesoporous metal–organic frameworks obtained by ion-exchange induced single-crystal to single-crystal transformation 
Qingxia Yao ,  Junliang Sun ,  Kuo Li ,  Jie Su ,  Maxim V. Peskov and Xiaodong Zou  
Dalton Trans., 2012, 41, 3953-3955 DOI: 10.1039/C2DT12088G     

Highly-connected, porous coordination polymers based on [M4(µ3-OH)2] (M = CoII and NiII) clusters: different networks, adsorption and magnetic properties 
Qing Chen ,  Wei Xue ,  Jian-Bin Lin ,  Rui-Biao Lin ,  Ming-Hua Zeng and Xiao-Ming Chen  
Dalton Trans., 2012, 41, 4199-4206 DOI: 10.1039/C2DT12022D     

Functional porphyrinic metal–organic frameworks: crystal engineering and applications 
Chao Zou and Chuan-De Wu  
Dalton Trans., 2012, 41, 3879-3888 DOI: 10.1039/C2DT11989G     

Synthesis and characterization of a new porphyrin–polyoxometalate hybrid material and investigation of its catalytic activity 
Mehdi Araghi ,  Valiollah Mirkhani ,  Majid Moghadam ,  Shahram Tangestaninejad and Iraj Mohammdpoor-Baltork  
Dalton Trans., 2012, 41, 3087-3094 DOI: 10.1039/C2DT11865C     

A copper thiolate centre for electron transfer: mononuclear vs. dinuclear complexes 
Marcello Gennari ,  Jacques Pécaut ,  Marie-Noëlle Collomb and Carole Duboc  
Dalton Trans., 2012, 41, 3130-3133 DOI: 10.1039/C2DT12355J   
 
Sequential self-assembly in metal–organic frameworks 
Brandon J. Burnett and Wonyoung Choe  
Dalton Trans., 2012, 41, 3889-3894 DOI: 10.1039/C2DT12103D  
   

Synthesis of porous aromatic framework with tuning porosity via ionothermal reaction 
Wei Wang ,  Hao Ren ,  Fuxing Sun ,  Kun Cai ,  Heping Ma ,  Jianshi Du ,  Huijun Zhao and Guangshan Zhu  
Dalton Trans., 2012, 41, 3933-3936 DOI: 10.1039/C2DT11996J     

A fluorescence “turn-on” chemodosimeter for Cu2+ in aqueous solution based on the ion promoted oxidation 
Junbo Li ,  Yang Zeng ,  Qihui Hu ,  Xianglin Yu ,  Jia Guo and Zhiquan Pan  
Dalton Trans., 2012, 41, 3623-3626 DOI: 10.1039/C2DT12497A     

Why not take a look at the articles today and blog your thoughts and comments below.

Fancy submitting an article to Dalton Transactions? Then why not submit to us today or alternatively email us your suggestions.

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Ion Uptake and Solid Solution Formation

The study of ion-mineral interactions is a fascinating topic which spans many disciplines from inorganic chemistry to geology and ancient history. The driving forces behind the interaction of an ion and a mineral are complex, and whether or not an ion becomes incorporated into the solid phase is determined by many factors.

celestite strontianite Eu3+ Cm3+ Eu Cm solid solution solid-solution

 This Hot paper by Kiel Holliday et al. looks at the coordination of Eu and Cm to investigate what role local symmetry, ligand strength and a range of other parameters have in solid solution formation in both Eu- and Cm-doped strontianite and celestite.

So what is solid solution formation dependent on and what factors influence it?

Discriminating factors affecting incorporation: comparison of the fate of Eu3+–Cm3+ in the Sr carbonate–sulfate system
Kiel Holliday, Aurélie Chagneau, Moritz Schmidt, Francis Claret, Thorsten Schäfer and Thorsten Stumpf
Journal Article
Dalton Trans., 2012, 41, 3642-3647
DOI: 10.1039/C2DT12425D

You can also keep up to date with the latest information by following us on twitter or siging up to our e-alert service.

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