Dalton Transactions Blog

When metal nanoparticles are used as catalysts, they can have a tendency to aggregate. Especially when the metal nanoparticles (NPs) are not functionalized as there isn’t anything to oppose the Van der Waals forces. Aggregation or coalescence of the NPs can lead to a decrease in catalytic activity. Two strategies have been developed for stabilisation — addition of a ligand post NP synthesis or inclusion of a coordinating ligand into the cation of an ionic liquid (IL).

In a previous Dalton Transactions article, (Dalton Trans., 2011, 40, 4660–4668) the stability of ruthenium nanoparticles (RuNPs) was improved by the combination of ILs and stabilising ligands to produce a recyclable catalytic system for the hydrogenation of toluene. In this new article, Agilio Padua and colleagues have taken this one step further and  investigated the effect of various ligands on the catalytic activity of RuNPs in an IL.

RuNPs were prepared in an IL, and in the presence and absence of a series of different ligands. Padua and colleagues discover that the activity of RuNPs with respect to the catalytic hydrogenation of cyclohexadiene, styrene and limonene increased with σ-donor ligands (water and octylamine) but decreased with π-acceptor ligands (carbon monoxide,  phenylphosphine and diphenylphosphine). This paper demonstrates how RuNPs as catalysts are remarkably similar to homogenous catalysts in that their activity and selectivity can be controlled by σ-donor and π-acceptor ligands.

Download the full paper to find out more…

Anhydrous metal halides and their soluble Lewis base-adduct relatives are ubiquitous starting materials in inorganic and organometallic chemistry, serving as extremely versatile precursors to myriad derivatives.  As a result, reliable and straight-forward protocols for accessing such species allow researchers to deploy their carefully crafted ligands and explore unexpected reactivity, as well as fully unveil the richness of previously reported systems.

Indeed, only a handful of thorium(IV) halide starting materials are commonly utilized, and as thorium turnings are becoming increasingly hard to come by, new routes to anhydrous thorium(IV) halides from available thorium(IV) salts are crucial. Jaqueline Kiplinger and co-workers have recently reported a facile synthesis of ThI₄(dme)₂ and have demonstrated its keen ability to be derivatized. As molecular actinide iodide complexes have been shown to offer markedly differing reactivities from their chloride counterparts, this contribution may allow for yet unseen reactivity at Th(IV) centres, and maybe even provide less tumultuous access to the exceptionally rare Th(III) oxidation state.

Check out the full article to read more about this new precursor and related complexes:

Thorium-mediated ring-opening of tetrahydrofuran and the development of a new thorium starting material: preparation and chemistry of ThI₄(DME)₂
Nicholas Travia, Marisa Monreal, Brian Scott and Jaqueline Kiplinger,
Dalton Transactions, 2012

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

Recent progress in the synthesis of inorganic nanoparticles 
C. N. R. Rao ,  H. S. S. Ramakrishna Matte ,  Rakesh Voggu and A. Govindaraj 
Dalton Trans., 2012,41, 5089-5120 DOI: 10.1039/C2DT12266A  

A one-dimensional coordination polymer constructed from planar pentanuclear copper(ii) clusters with a flexible tripodal ligand 
Qilong Zhu ,  Chaojun Shen ,  Chunhong Tan ,  Tianlu Sheng ,  Shengmin Hu and Xintao Wu  
Dalton Trans., 2012,41, 9604-9606 DOI: 10.1039/C2DT30912B 
 
Nothing frustrating about “Frustrated Lewis pairs” 
Douglas W. Stephan  
Dalton Trans., 2012,41, 9015-9015 DOI: 10.1039/C2DT90093A  

Pushing the frontiers in polyoxometalate and metal oxide cluster science 
De-Liang Long and Leroy Cronin  
Dalton Trans., 2012,41, 9815-9816 DOI: 10.1039/C2DT90121H  

Synthesis of facial cyclometalated iridium(iii) complexes triggered by tripodal ligands 
Toshiyuki Moriuchi ,  Lisheng Mao ,  Hsyueh-Liang Wu ,  Satoshi D. Ohmura ,  Masami Watanabe and Toshikazu Hirao  
Dalton Trans., 2012,41, 9519-9525 DOI: 10.1039/C2DT12309F  

Controlled association of single-molecule magnets (SMMs) into coordination networks: towards a new generation of magnetic materials 
Ie-Rang Jeon and Rodolphe Clérac  
Dalton Trans., 2012,41, 9569-9586 DOI: 10.1039/C2DT30906H  

Metal-directed assembly of chiral bis-Zn(ii) Schiff base structures 
Martha V. Escárcega-Bobadilla ,  Daniele Anselmo ,  Sander J. Wezenberg ,  Eduardo C. Escudero-Adán ,  Marta Martínez Belmonte ,  Eddy Martin and Arjan W. Kleij  
Dalton Trans., 2012,41, 9766-9772 DOI: 10.1039/C2DT30642E  

Cyclometalated ruthenium(ii) complexes with a bis-carbene CCC-pincer ligand 
You-Ming Zhang ,  Jiang-Yang Shao ,  Chang-Jiang Yao and Yu-Wu Zhong  
Dalton Trans., 2012,41, 9280-9282 DOI: 10.1039/C2DT31015E  

Enhanced stability and CO2 affinity of a UiO-66 type metal–organic framework decorated with dimethyl groups 
Yuting Huang ,  Weiping Qin ,  Zhong Li and Yingwei Li  
Dalton Trans., 2012,41, 9283-9285 DOI: 10.1039/C2DT30950E  

Post-modification of a MOF through a fluorescent-labeling technology for the selective sensing and adsorption of Ag+ in aqueous solution 
Lejie Zhang ,  Yuan Jian ,  Jian Wang ,  Cheng He ,  Xuezhao Li ,  Tao Liu and Chunying Duan  
Dalton Trans., 2012,41, 10153-10155 DOI: 10.1039/C2DT30689A  

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

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We are very pleased to announce that the first Gold for Gold open access article has been published in Dalton Transactions. The Gold for Gold initiative was recently launched and rewards UK RSC Gold subscribers with credits to publish their RSC articles via Open Science, the RSC’s Gold Open Access option. The article by Stephen J. Archibald et al. is free to download to all

CXCR4 chemokine receptor antagonists: nickel(II) complexes of configurationally restricted macrocycles
Rachel Smith , Dana Huskens, Dirk Daelemans, Ryan E. Mewis, Courtney D. Garcia, Amy N. Cain, TaRynn N. Carder Freeman, Christophe Pannecouque, Erik De Clercq, Dominique Schols, Timothy J. Hubin and Stephen J. Archibald
Dalton Trans., 2012, 41, 11369-11377
DOI: 10.1039/C2DT31137B 

More information on Gold for Gold is available on our website. If you have any further questions on the procedure, or are an interested customer from outside the UK, please contact us.

Cyanide compounds can be highly toxic as the cyanide anion inhibits an enzyme in the electron transport chain, cytochrome c oxidase. The inhibition of this enzyme means that cells in the body can no longer produce ATP aerobically for energy which can eventually affect the heart and the central nervous system.

Some  industrial processes such as gold mining make use of cyanide ions and the accidental release of these ions can cause serious problems. The potassium salt of cyanide is also used as a terror chemical agent. As such, there is a need for more efficicent detection of cyanide ions with lower detection limits than methods which have been used previously.

Manoj Kumar and his team at Guru Nanak Dev University, India have synthesized a triazole ( five membered ring with 3 nitrogen and 2 carbon atoms) modified triphenylene (four fused benzene rings) which can selectively complex copper²⁺ ions.

The triphenylene based copper ensemble was shown using UV-vis and fluorescence spectroscopy to give a selective response for cyanide ions, even in the presence of blood serum and bovine serum albumin. This paper highlights the potential versatility of the copper ensemble for cyanide detection in different environments.

To read more about the detection of sodium cyanide in tap water and solid state detection of cyanide using the copper ensemble read the full article.

Triphenylene based copper ensemble for the detection of cyanide ions
Vandana Bhalla ,  Hardev Singh and Manoj Kumar
Dalton Trans., 2012