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Forming trifluoromethylmetallates: competition between decarboxylation and C–F bond activation of group 11 trifluoroacetate complexes, [CF3CO2ML]–
Nicole J. Rijs and Richard A. J. O’Hair
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT12117D
Ferrocene is a sandwich complex of two cyclopentadienyl (Cp) units bound to an Fe centre and is probably the most famous organometallic compound containing a Cp ligand. There are a huge variety of organometallic complexes with a range of metal centres and ligands and there is a great deal of interest in their structural, chemical and physical properties.
This Hot Article details the preparation of a series of [(η7-C7H7)Zr(η5-L)] (L = Cp and Ind) complexes and their structural characterisation. The authors use this information to develop a system to measure the steric bulk of Cp ligands………..so how big is a Cp?
To find out, you can download this article now, which is free to access for 4 weeks
How big is a Cp? Cycloheptatrienyl zirconium complexes with bulky cyclopentadienyl and indenyl ligands
Andreas Glöckner, Heiko Bauer, Miyuki Maekawa, Thomas Bannenberg, Constantin G. Daniliuc, Peter G. Jones, Yu Sun, Helmut Sitzmann, Matthias Tamm and Marc D. Walter
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT12132H
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If you’re interested in finding out more about MOFs, and in particular those based on metalloporphyrins, then look no further… Chao Zou and Chuan-De Wu’s recent Perspective article provides an interesting overview of these functional materials. The researchers from Zhejiang University, China, discuss synthetic strategies and applications ranging from hydrogen storage to photocatalysis. Although the application of porphyrinic MOFs is considerably underdeveloped compared to other porphyrinic materials, say Zou and Wu, this article demonstrates that metalloporphyrins are an ideal choice for designing crystalline solid frameworks.
To read more, download the article now – it’s free to access.
Functional porphyrinic metal–organic frameworks: crystal engineering and applications
This Perspective article is part of the upcoming themed issue on Coordination Chemistry in the Solid State, guest edited by Dalton Transactions Associate Editor, Russell Morris. Keep your eyes peeled for many of our other coordination chemistry articles which have already been published, including Burnett and Choe’s Perspective article on “Sequential self-assembly in metal–organic frameworks”.
Edward Tiekink is based at the University of Malaya
Edward Tiekink gives us a concise overview of drug developments involving selenium and tellurium compounds in this Dalton Transactions Frontier.
Download it today, whilst it is still free….
Therapeutic potential of selenium and tellurium compounds: Opportunities yet unrealised
Edward R. T. Tiekink
Dalton Trans., 2012
DOI: 10.1039/C2DT12225A
Why not take a look at some of Edward Tiekink’s other recent articles:
The metal–carbonyl···π(aryl) interaction as a supramolecular synthon for the stabilisation of transition metal carbonyl crystal structures
Julio Zukerman-Schpector, Ionel Haiduc and Edward R.T. Tiekink
Chem. Commun., 2011, 47, 12682-12684
DOI: 10.1039/C1CC15579B, Communication
Interwoven coordination polymers sustained by tautomeric forms of the bridging ligand
Pavel Poplaukhin and Edward R. T. Tiekink
CrystEngComm, 2010, 12, 1302-1306
DOI: 10.1039/B916585A, Paper
Jie-Sheng Chen and colleagues from Shanghai Jiao Tong University report the synthesis of a Pd/Fe3O4 nanocomposite that can be used as a heterogeneous catalyst for the hydrogenation of p-nitrophenol. Convenient recycling of the catalyst using a magnet is possible – find out more by downloading the article whilst it’s free to access:
Controlled synthesis of magnetic Pd/Fe3O4 spheres via an ethylenediamine-assisted route
Hai-Qun Wang, Xiao Wei, Kai-Xue Wang and Jie-Sheng Chen
Dalton Trans., 2012
DOI: 10.1039/C2DT12278B
A team of researchers have determined the structure of metastable compound Bi2MnxAl7−xO14, an intermediate phase in the decomposition of mullite-Bi2MnxAl4-xO9+δ, using a strategy that included the use of a charge-flipping algorithm and Monte-Carlo based simulations. The strategy may be particularly useful in situations where it is difficult to get high quality crystals.
The article is currently free so download it today.
Mullite-derivative Bi2MnxAl7−xO14 (x ~ 1): structure determination by powder X-ray diffraction from a multi-phase sample
Tao Yang, Vaclav Petricek, Wei Wan, Zidong Wei and Junliang Sun
Dalton Trans., 2012
DOI: 10.1039/C2DT11855F
This Hot Article from the University of Western Ontario by Laura C. Pavelka and Kim M. Baines details some interesting cycloaddition reactions of phosphaalkenes with alkynes.
Reactions of this type have not been well studied and typically require electron rich alkynes and quite specialised phosphoalkenes for the reaction to proceed. Here the authors have developed a much simpler approach to the syntheses using readily available reagents and a more direct route, allowing them to produce a variety of 1,2-dihydrophosphinines in good yields.
To find out how, you can download their article which is free to access for the next 4 weeks
Facile synthesis of luminescent benzo-1,2-dihydrophosphinines from a phosphaalkene
Laura C. Pavelka and Kim M. Baines
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT11690A
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A team of researchers have synthesised an iron(II) bispyrazolylpyridine complex in order to elucidate the interplay between spin transition and polymorphism.
Complexes demonstrating high spin–low spin crossover could prove to be very useful materials in technologies which rely on switching mechanisms, however, to use them to their full potential, any properties affecting their performance need to be understood – crystal symmetry being one of them. Mario Ruben and co-workers discovered that crystallisation of the iron(II) bispyrazolylpyridine complex produced two polymorphs which upon heating, yields a third polymorphic form. Interestingly, the different polymorphs each demonstrate different magnetic behaviour.
Whilst one polymorph, exhibits an abrupt, hysteretic high/low spin transition, the other remains low spin. The team have attributed this to varying levels of inter-molecular cooperativity within the crystal structures.
To read more, download the Dalton Transactions article now…
The interplay of iron(II) spin transition and polymorphism
Ivan Šalitroš, Olaf Fuhr, Andreas Eichhöfer, Robert Kruk, Ján Pavlik, Lubor Dlháň, Roman Boča and Mario Ruben
Cisplatin is a well known chemotherapy drug used to treat a range of cancers. While the drug can be an effective treatment there are notable unwanted side-effects, which can include nausea, vomiting, kidney damage and loss of hearing. This new research from Leeds University by Charlotte Willans et al. details the activity of a range of silver complexes containing N-heterocyclic carbene (NHC) ligands which show comparable and even enhanced cytotoxicity compared to cisplatin. As the compounds don’t contain platinum they are likely to be less toxic and therefore exhibit fewer and less severe side-effects.
The team synthesised a series of monodentate, bidentate and macrocyclic cationic silver bis(NHC) complexes and tested their activity with cell lines of breast and colon cancer (MCF7 and DLD1 lines respectively). They found that the bidentate complexes showed enhanced cytotoxicity over the monodentate and macrocyclic ligands, which were similar to cisplatin. As yet the exact mechanisms of action are still unclear but are likely linked to the stabilities of the complexes.
For more information about this exciting research you can download the article which is free to access for 4 weeks. You can also keep up to date with all the latest news in inorganic chemistry by following us on twitter or signing up to the Dalton Transactions e-alert service.
Enhanced cytotoxicity of silver complexes bearing bidentate N-heterocyclic carbene ligands
Charlotte E. Willans, Diana C F Monteiro, Roger M Phillips, Benjamin D Crossley and Jake Fielden
Dalton Trans., 2012, Accepted Manuscript
DOI: 10.1039/C2DT12399A
Also of interest from the collection ‘Highlights in Chemistry’
Therapeutic applications of gold complexes: lipophilic gold(III) cations and gold(I) complexes for anti-cancer treatment
Chi-Ming Che and Raymond Wai-Yin Sun
Chem. Commun., 2011, 47, 9554-9560
DOI: 10.1039/C1CC10860C, Highlight
The need for a hydrogen storage material that can store hydrogen reversibly, with little or no kinetic barrier, and at ambient conditions remains a great challenge for researchers in this field. In order to progress towards a future hydrogen economy, hydrogen storage materials must also be practical for mobile applications and of course be economically viable.
Many different materials have been proposed for hydrogen storage. These range from physisorption materials such as activated carbons, zeolites and Metal Organic Frameworks (MOFs) to materials based on chemisorption such as metal hydrides, ammonia boranes and alanates. The hydrogen binding mechanism of chemisorption materials is through the formation of strong covalent bonds with hydrogen and so even though they have high hydrogen storage capacities, the drawback is that due to their high hydrogen binding enthalpies, the materials must be heated to remove H2.
To improve the unfavorable thermodynamics and poor kinetics of complex hydrides, researchers have successfully applied a ‘multicomponent’ strategy whereby two compounds are mixed together to form a multinary phase. The mixed LiNH2–MgH2 system is a successful example of the employment of the ‘multicomponent’ strategy to improve the characteristics of complex hydrides for hydrogen storage. Applying this method to metal amidoborane systems is an exciting prospect.
With this in mind, Chen et al. synthesized a Li–Na mixed amidoborane, Na[Li(NH2BH3)2] using a wet-chemical method. Using first-principles techniques, the team were able to explore the likelihood of the existence of multicomponent Li–Na amidoboranes with varying Li/Na ratios. They discovered that the dehydrogenation temperature of Na[Li(NH2BH3)2] is lower than that of lithium or sodium amidoboranes and determined that this could be due to a stronger dihydrogen bond interaction and a moderate hydrogen atom removal energy. They also proposed the mechanism for the first-step dehydrogenation.
To find out more, read the Dalton Transactions full paper…
Li–Na ternary amidoborane for hydrogen storage: experimental and first-principles study
Wen Li, Ling Miao, Ralph H. Scheicher, Zhitao Xiong, Guotao Wu, C. Moysés Araújo, Andreas Blomqvist, Rajeev Ahuja, Yuanping Feng and Ping Chen
DOI: 10.1039/C2DT11819J
