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

05 Apr 2012

Computational studies of complexation of nitrous oxide by borane–phosphine frustrated Lewis pairs Thomas 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

05 Apr 2012

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.

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

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HOT Article: Role of Zn and Mn in Parkinson’s Disease

03 Apr 2012

Model of the YPK9 protein In 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

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Exchanging ligands on semiconducting nanocrystals

30 Mar 2012

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

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

28 Mar 2012

Amine 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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Ion Uptake and Solid Solution Formation

26 Mar 2012

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.

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

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Vapour sorption with no loss of crystallinity

23 Mar 2012

A recent article from John Field and his team at the University of KwaZulu-Natal, South Africa, describes the sorption and sensing properties of a porous material with an unusual crystal structure. The platinum based material has an open framework made up from repeating 2D stacks of [Pt{4′-(Ph)trpy}(NCS)]⁺ cations (where trpy is 2,2′:6′,2″-terpyridine) that are stabilised by extended π-π interactions. This is somewhat different to the usual coordination compounds that are formed from metal ions linked by bridging organic molecules.

Unlike it’s parent material ([Pt(trpy)(NCS)]SbF₆), this compound can reversibly sorb and desorb organic vapours with no disruption of the framework structure which the team attribute to the 4′-phenyl substituent which participates in stabilising π-π interactions with pyridines on the nearby cations.

The solvent accessible voids in [Pt{4′-(Ph)trpy}(NCS)]SbF₆

Read this HOT article now:
Sorption of small molecule vapours by single crystals of [Pt{4′-(Ph)trpy}(NCS)]SbF₆ where trpy = 2,2′:6′,2′′-terpyridine: a porous material with a structure stabilised by extended π–π interactions
John S. Field, Orde Q. Munro and Bradley P. Waldron

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Linking up with Mercury

14 Mar 2012

Species featuring group 12 to group 12 bonds have lately become the subject of much interest and discussion, as have species containing homo-nuclear metal to metal bonds. This Hot Communication from Paul Weiss, Shiv Khanna, Ayusman Sen and colleagues details the discovery of a dimeric zintl anion featuring an Hg-Hg bond.

Molecular orbital diagram of the dimeric zintl ion

The new zintl phase contains [As₇HgHgAs₇]⁴⁻ ions with an unsupported Hg-Hg bond, as characterized by cyclic voltammetry, molecular orbital diagram, band gap energy and Raman spectra. To find out more about the group’s findings you can download there paper below, which is free to access for 4 weeks.

On the stability of an unsupported mercury–mercury bond linking group 15 Zintl clusters
Sukhendu Mandal, Arthur C. Reber, Meichun Qian, Ran Liu, Hector M. Saavedra, Saikat Sen, Paul S. Weiss, Shiv N. Khanna and Ayusman Sen
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT30083D

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Hot Article: Iron Chelators for Iron Overload

14 Mar 2012

Iron is a biological necessity and the amount we take-in must be carefully controlled – normally this isn’t a problem as eating a varied, healthy diet provides us with the nutrients we need. Once we have an adequate concentration of iron our intestines then stop absorbing it, preventing a surplus building up.

Fe chelating ligand

This absorption control is usually very effective as eating and drinking is our main source of iron, however after a blood transfusion excess iron can be introduced into the body and there is no natural mechanism to remove the unwanted metal ions. Some diseases such as Diamond–Blackfan anemia or β-thalassemia can require regular treatment by blood transfusion, which can lead to acute iron overload. This can be very harmful as iron can build up in vital organs such as the heart and liver and cause irreversible organ damage.

Iron chelating agents offer a treatment for Fe overload by binding to the excess iron ions, allowing them to be safely excreted before they build up and cause damage to the body. This Hot Article by Professor Des Richardson and Professor Paul Bernhardt et al. details the synthesis and characterisation of a series of dithiocarbazate Schiff base analogues for their suitability as iron chelators. Schiff bases are previously known as chelation ligands, but the derivatives detailed here show some interesting biological activities…

Heterocyclic dithiocarbazate iron chelators: Fe coordination chemistry and biological activity
Maram T. Basha, Jy D. Chartres, Namfon Pantarat, Mohammad Akbar Ali, Aminul Huq Mirza, Danuta S. Kalinowski, Des R. Richardson and Paul V. Bernhardt
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT12387H

This article will be part of our upcoming themed issue on Metals in Medicine: Non-Cancer Therapeutics – other hot papers due to be published in this special themed issue include the HOT Article: Anti-microbials that target destabilised DNA and the Hot Perspective: Treating Wilsons Disease.

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Cerium cation behaviour could change water splitting studies

13 Mar 2012

Scientists in Germany and Japan have shown that cerium(IV) predominantly forms a dinuclear complex in aqueous solution. Until now, scientists had thought that tetravalent cerium was a monomeric species in aqueous solution. The finding could have important implications for scientists studying water oxidation.

Atsushi Ikeda-Ohno from the Helmholtz-Zentrum Dresden Rossendorf, Dresden, and colleagues used a combination of extended X-ray absorption fine structure and density functional theory calculations to study the cerium(IV) cation. ‘In an aqueous solution, the primary form of metal cations is generally a simple mononuclear hydrate complex or a mononuclear oxo-cation,’ says Ikeda-Ohno, ‘but cerium(IV) forms a unique oxo- or/and hydroxo-bridging dinuclear complex.’

A combined X-ray absorption spectroscopy and density functional calculation study has revealed that a single oxo-bridging dinuclear complex is the dominant form of soluble Ce(IV) species in an aqueous perchloric acid solution.

‘We have always assumed that any reaction between a catalyst and a cerium salt is a one electron transfer reaction,’ says Curtis Berlinguette from the University of Calgary, Canada, who studies the mechanistic behaviour of homogeneous water oxidation catalysts using cerium salts as the terminal oxidant. ‘But if cerium(IV) does exist as a dimer and has an oxo bridge, then it really does question these assumptions and, more importantly, the nature of the oxygen-oxygen bond formation step.’

Berlinguette explains that the current assumption is that you make a catalyst with the metal oxo unit and that reacts with water. But, if the cerium salt that exists in solution contains an oxo, then you could potentially have a combination between the cerium(IV) oxo and the metal oxo, producing oxygen. Therefore, what might appear to be a water oxidation catalyst is in fact just forming dioxygen through reaction with the cerium salt.

‘It would be really interesting if Ikeda-Ohno’s team could extend this study to the acidic conditions and concentrations that are more widely used by the homogeneous catalytic water oxidation community. Then we will have much more insight into what species we are actually studying in solution,’ says Berlinguette.

Ikeda-Ohno says that developing time-resolved systems for X-ray techniques to probe the reactions of the cerium(IV) is the team’s next challenge.

Written by Rachel Cooper

Dinuclear complexes of tetravalent cerium in an aqueous perchloric acid solution
Atsushi Ikeda-Ohno, Satoru Tsushima, Christoph Hennig, Tsuyoshi Yaita and Gert Bernhard
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C2DT12406H

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