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February’s HOT articles

05 Feb 2013

Solvent-modified dynamic porosity in chiral 3D kagome frameworks
Tony D. Keene, Damien Rankine, Jack D. Evans, Peter D. Southon, Cameron J. Kepert, Jade B. Aitken, Christopher J. Sumby and Christian J. Doonan

Solvent-modified dynamic porosity in chiral 3D kagome frameworks

Photoinduced charge transfer involving a MoMo quadruply bonded complex to a perylene diimide
Brian G. Alberding, Samantha E. Brown-Xu, Malcolm H. Chisholm, Arthur J. Epstein, Terry L. Gustafson, Sharlene A. Lewis and Yong Min

Spectral signature of a Ru(II, III, IV) complex: a combined experimental and theoretical investigation
Jacques Bonvoisin and Ilaria Ciofini

Electronic structure and soft-X-ray-induced photoreduction studies of iron-based magnetic polyoxometalates of type {(M)M₅}₁₂Fe^III₃₀ (M = Mo^VI, W^VI)
Karsten Kuepper, Christine Derks, Christian Taubitz, Manuel Prinz, Loïc Joly, Jean-Paul Kappler, Andrei Postnikov, Wanli Yang, Tatyana V. Kuznetsova, Ulf Wiedwald, Paul Ziemann and Manfred Neumann

Palladium complexes with stabilized germylene and stannylene ligands
Marina M. Kireenko, Kirill V. Zaitsev, Yuri F. Oprunenko, Andrei V. Churakov, Viktor A. Tafeenko, Sergey S. Karlov and Galina S. Zaitseva

Heterolytic activation of dihydrogen by platinum and palladium complexes
Karina Q. Almeida Leñero, Yannick Guari, Paul C. J. Kamer, Piet W. N. M. van Leeuwen, Bruno Donnadieu, Sylviane Sabo-Etienne, Bruno Chaudret, Martin Lutz and Anthony L. Spek

Highly fluorescent complexes with gold, palladium or platinum linked to perylene through a tetrafluorophenyl group
Sergio Lentijo, Gabriel Aullón, Jesús A. Miguel and Pablo Espinet

The Tolman electronic parameter (TEP) and the metal–metal electronic communication in ditopic NHC complexes
Dmitry G. Gusev and Eduardo Peris

A different route to functional polyolefins: olefin–carbene copolymerisation
Nicole M. G. Franssen, Joost N. H. Reek and Bas de Bruin

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Remarkable stability demonstrated by tungstenacyclobutadiene complexes

30 Jan 2013

Adam Veige and colleagues from the University of Florida, USA, report the successful isolation of the neutral ONO^3- trianionic pincer-type tungsten alkylidyne complex [CF₃–ONO]WΞC(^tBu)(OEt₂).

Cyclooctyne, which is normally polymerised due to its internal ring strain, reacts rapidly with the pincer-type tungsten alkylidyne complex to give the first example of a bicyclic metallacyclobutadiene. The pincer-type tungsten alkylidyne complex was also treated with alkyne substrates 1-phenylpropyne and 4,4-dimethyl-2-pentyne to give two more tungstenacyclobutadienes. The three tungstenacyclobutadienes made in this study all exhibit incredible stability.

Download the paper today to read how the team have explored the factors contributing to this stability.

Unusually stable tungstenacyclobutadienes featuring an ONO trianionic pincer-type ligand
Matthew E. O’Reilly, Ion Ghiviriga, Khalil A. Abboud and Adam S. Veige
Dalton Trans., 2013
DOI: 10.1039/C2DT32653A

You might also be interested in this Dalton Transactions article by the same authors:

The influence of reversible trianionic pincer OCO³⁻μ-oxo Cr^IV dimer formation ([Cr^IV]₂(μ-O)) and donor ligands in oxygen-atom-transfer (OAT)
Matthew E. O’Reilly, Trevor J. Del Castillo, Khalil A. Abboud and Adam S. Veige
Dalton Trans., 2012,41, 2237-2246
DOI: 10.1039/C1DT11104C, Paper

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Crystal structure of a face-sharing fluoroaluminate anion

30 Jan 2013

Fluorides of aluminium are used in the aluminium industry and also as catalysts for ozone friendly alternatives to chlorofluorocarbons (CFC’s). Previously, crystal structures of some fluoroaluminate anions have been solved by the introduction of either organic or metal cations. But until now, the crystal structure of a particular fluoroaluminate anion, the bioctahedral Al₂F₉^3- anion had not been reported.

The crystal structure of this anion has recently been solved by Rika Hagiwara and colleagues at Kyoto University. They first synthesized the compound, [C₁₈MIm][AlF₄] (1-methyl-3-octadecylimidazolium tetrafluoroaluminate) and discovered that slow evaporation of the chloroform solution gave transluscent crystals of [C₁₈MIm]₃[Al₂F₉](CH₂Cl₂)_n. It is thought that this species was formed by the reaction below:

3[C₁₈MIm][AlF₄] + nCH₂Cl₂ → [C₁₈MIm]₃[Al₂F₉](CH₂Cl₂)_n + AlF₃

The Al₂F₉^3-anion has two octahedral AlF₆ units which are face-sharing and has D_3h symmetry.

To find out more, read the full Dalton Transactions article:

The first crystallographic example of a face-sharing fluoroaluminate anion Al₂F₉³⁻
Fei Xu, Kazuhiko Matsumoto and Rika Hagiwara

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Meet us in 2013

14 Jan 2013

With the start of the calendar year, its as good a time as any to get thinking about where our 2013 travels will take us…

We are planning to attend the following conferences. Will you be there too?

245^th ACS National Meeting & Exposition, New Orleans, USA, 7th April 2013
96^th Canadian Chemistry Conference and Exhibition, Québec, Canada, 26th May 2013
23^rd North American Catalysis Society meeting, Louisville, USA, 2nd June 2013
10^th Congress on Catalysis Applied to Fine Chemicals, Turku, Finland, 16th June 2013
20^th EuCheMS Conference on Organometallic Chemistry, 30th June 2013, St Andrews, UK
Gordon Research Conference: Organometallic Chemistry, Newport, Rhode Island, USA, 8th July 2013
EuropaCat 2013, Lyon, France, 1st September 2013
246^th ACS National Meeting & Exposition, Indianapolis, USA, 8th September 2013

Please do let us know if you think you’ll be attending – we’d love to meet you!
	Jamie Humphrey, Editor	Fiona McKenzie, Deputy Editor

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Step-wise heterometallic cluster synthesis enables tuning of magnetic properties

11 Jan 2013

Scientists in Italy and Brazil report a new synthesis for making heteronuclear propeller-like single molecule magnets (SMMs) that could be used to design structures with a variety of d- and f-block metals and R groups, yielding 100% pure complexes without metal scrambling.

There is considerable interest in manipulating SMMs to have higher ground spin states, enhanced magnetic properties and increased robustness for possible future applications in quantum computing. In this study, Roberta Sessoli and colleagues use a central chromium(III) ion in their synthesis of Fe₃Cr propeller-like aggregates to show that molecular ground spin state can be altered by selectively changing the spin state of the metal ion.

The chemically inert chromium(III) produces a kinetically stable central “core” which then combines with the dimeric iron(III) starting material to give propeller-like complexes

The synthetic method could potentially be tailored to produce propeller-like SMMs with particular properties.

Read more about the synthesis for free at…

A new approach to the synthesis of heteronuclear propeller-like single molecule magnets
Pasquale Totaro, Kátia Cristina M. Westrup, Marie-Emmanuelle Boulon, Giovana G. Nunes, Davi F. Back, Andersson Barison, Samuele Ciattini, Matteo Mannini, Lorenzo Sorace, Jaísa F. Soares, Andrea Cornia and Roberta Sessoli
Dalton Trans., 2013
DOI: 10.1039/C2DT32618C

Here are some other Dalton Transactions articles by the same authors:

Lanthanides in molecular magnetism: so fascinating, so challenging
Javier Luzon and Roberta Sessoli
Dalton Trans., 2012, 41, 13556-13567
DOI: 10.1039/C2DT31388J, Perspective
From themed issue Frontier and Perspectives in Molecule-Based Quantum Magnet

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, 8368-8378
DOI: 10.1039/C2DT30172E, Paper

Dimers and chains of {3d–4f} single molecule magnets constructed from heterobimetallic tectons
Traian D. Pasatoiu, Mael Etienne, Augustin M. Madalan, Marius Andruh and Roberta Sessoli
Dalton Trans., 2010, 39, 4802-4808
DOI: 10.1039/B925425K, Paper
From themed issue Molecular magnets

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IUPAC Provisional Recommendations on Metal-Organic Framework and Coordination Polymer Terminology

08 Jan 2013

The IUPAC task group: Coordination polymers and metal organic frameworks: terminology and nomenclature guidelines have published provisional recommendations. The article can be accessed directly here and any comments can be directed to the task group chair, Professor Lars Öhrström.

The task group was set-up in 2009 to document, analyse and evaluate the use of nomenclature and terminology in the areas of coordination polymers and metal-organic frameworks. As well as meeting on three occasions the group also published a Highlight article detailing the need for terminology guidelines and the provisional recommendations, which include the following definitions:

Term	Definition
Coordination Polymer	A coordination compound continuously extending in 1, 2 or 3 dimensions through coordination bonds
Coordination Network	A coordination compound extending, through coordination bonds, in 1 dimension, but with cross-links between two or more individual chains, loops or spiro-links, or a coordination compound extending through coordination bonds in 2 or 3 dimensions
Metal-Organic Framework	Metal-Organic Framework, abbreviated to MOF, is a Coordination Polymer (or alternatively Coordination Network) with an open framework containing potential voids

There are also recommendations on net and network topology, topology descriptors, nomenclature and the use of other terms (which explicitly discourages the term “hybrid organic-inorganic materials”)

Download the full article for the complete recommendations and take a look at the Highlight article published last year

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
DOI: 10.1039/C2CE06488J

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Dalton Discussion 14 – Advancing the chemistry of actinides

03 Jan 2013

Now welcoming abstract submissions for Dalton Discussion 14 – Advancing the Chemistry of Actinides

16^th–18^th September 2013, Edinburgh, UK

Confirmed speakers:	Geoff Cloke, University of Sussex, UK
	Melissa Denecke, Karlsruhe Institute of Technology, Germany
	Laurent Maron, Université Paul Sabatier, Toulouse, France
	Jeffrey Long, University of California, Berkeley, USA
	Nik Kaltsoyannis, University College London, UK
	Marinella Mazzanti, CEA, Grenoble, France
	Paula Diaconescu, University of California, Los Angeles, USA
	Jonathan Lloyd, University of Manchester, UK

This Dalton Discussion aims to highlight the burgeoning role, and exciting prospects for actinides in modern, metal-based chemistry. Abstracts for oral presentations must be sent in before 15^th February 2013.

Authors of the selected oral abstracts will then be expected to submit their work as a full paper, which will form the basis of their short presentation at the Discussion meeting. The paper itself must contain new, unpublished work and be submitted for review to the Editorial Office of Dalton Transactions by 16^th August 2013. At the conference, each author will be given approximately 5 minutes to summarise the key points of their paper in order to leave the majority of time open for discussion

This year, Dalton Discussion 14 is adopting a new process. Papers presented at Dalton Discussions will continue to be published in a dedicated themed issue of Dalton Transactions, however article peer-review will now take place after the Discussion. This means that speakers have longer to make the finishing touches to their article before the papers are made available online prior to the meeting.

To find out more about Dalton Discussion 14 and to submit your abstract, visit the dedicated RSC webpage.

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Phosphinimine-borane frustrated Lewis pairs

21 Dec 2012

The current issue of Dalton Transactions is a themed issue on boranes and borohydrides, of which one of the cover articles by Chunfang Jiang and Douglas W. Stephan explores phosphinimine-boranes in frustrated Lewis pair chemistry. Frustrated Lewis pairs are entities that consist of a Lewis acid and a Lewis base which, because of sterics, do not form an adduct. These systems are very reactive and are able to activate H₂, CO₂, and olefins amongst others without the need for a transition metal catalyst.

In this article, a series of phosphinimines (species contanining a phosphorous-nitrogen double bond) were combined with B(C₆F₅)₃ and in one case a Lewis acid-base adduct was formed. The reactivity of the adduct was compared to the other cases where frustrated Lewis pairs were generated. Remarkably, the researchers discovered that both the adduct and the frustrated Lewis pairs were able to activate H₂, CO₂ and phenylacetylene.

This work paves the way for discovering even more acid base combinations that could be used in frustrated Lewis pair systems for catalysis without the need for transition metals.

To find out more, read the full Dalton Transactions article:

Phosphinimine–borane combinations in frustrated Lewis pair chemistry
Chunfang Jiang and Douglas W. Stephan
Dalton Trans., 2013, 42, 630-637

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Divergent Activation Chemistry of Carbon Oxides at Uranium(III)

17 Dec 2012

Developing facile and economical technologies for utilizing CO and CO₂ as C1 building blocks remains a lucrative challenge, and this area has recently enjoyed a surge in interest and development. The current paradigm for activating these abundant carbon oxides invokes reduction of the strong C-O multiple bonds, typically facilitated by low-valent transition-metal and f-element complexes, to yield oligomerized ([CO_x]ⁿ^– )units or (CO)-incorporated organic materials.

Polly Arnold and co-workers have recently demonstrated that the discreet U(III) tris-amide complex [U(N(SiMe₃)₂)₃] is indeed a versatile reducing agent for such carbon oxide activation chemistry, cleanly reacting with CO to yield a stable ynediolate ([OCCO]^2-) adduct which features a newly formed C-C bond.

Reporting in Dalton Transactions, Arnold and co-workers now describe a modified U(III) platform which incorporates a hemi-labile, bidentate alkoxy-tethered NHC ligand, and divergent activation of carbon oxides at U(III). This report serves to underscore the potency of ligand design as an instrument for encouraging novel and unusual chemical transformations, in addition to describing a variety of new complexes incorporating activated carbon oxides.

Check out the full article to read more about these divergent carbon oxide activation pathways.

Carbon monoxide and carbon dioxide insertion chemistry of f-block N-heterocyclic carbene complexes
Polly L. Arnold, Zöe R. Turner, Anne I. Germeroth, Ian J. Casely, Gary S. Nichol, Ronan Bellabarba and Robert P. Tooze

Dalton Trans., 2013, Advance Article
DOI: 10.1039/C2DT31698F

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Unexpected interactions for piano-stool carbene complexes

07 Dec 2012

A team of researchers from France, Spain and Russia have put forward a case to explain a counter-intuitive conformation of manganese alkylalkoxycarbene complexes.

Using molecular orbitals, it is predicted that such complexes adopt a vertical coordination mode. This is largely the case – although one exception reported by Landman et al. earlier this year (see here) prompted the team to investigate what really is going on…

Coordination modes of carbene ligands in piano-stool complexes

Using a combination of DFT calculations and XRD analysis, Lugan et al. confirm that non-covalent interligand interactions between the alkyl substituents on the carbene and the carbon monoxide ligand (C-H^…C≡O) are responsible for these complexes adopting the unexpected horizontal coordination mode. Although such an interaction is weak, it goes to show that its enough to influence geometry.

Download the article now…

On the incidence of non-covalent intramolecular interligand interactions on the conformation of carbene complexes: a case study
Noël Lugan, Israel Fernández, Rémy Brousses, Dmitry A. Valyaev, Guy Lavigne and Nikolai A. Ustynyuk
Dalton Trans., 2013, Advance Article

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