Dalton Transactions Blog

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

When phosphorus and NHC (N-heterocyclic carbene) meet each other 
Sylvain Gaillard and Jean-Luc Renaud  
Dalton Trans., 2013, Advance Article DOI: 10.1039/C2DT32789A  

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  

Linear trinuclear Zn(II)–Ce(III)–Zn(II) complex which behaves as a single-molecule magnet 
Shiori Hino ,  Moe Maeda ,  Kei Yamashita ,  Yumiko Kataoka ,  Motohiro Nakano ,  Tomoo Yamamura ,  Hiroyuki Nojiri ,  Maiko Kofu ,  Osamu Yamamuro and Takashi Kajiwara  
Dalton Trans., 2013,42, 2683-2686 DOI: 10.1039/C2DT32812G  

Dinuclear mixed-valence CoIIICoII complexes derived from a macrocyclic ligand: unique example of a CoIIICoII complex showing catecholase activity 
Samit Majumder ,  Suraj Mondal ,  Pascale Lemoine and Sasankasekhar Mohanta  
Dalton Trans., 2013, Advance Article DOI: 10.1039/C2DT32629A  

A simple l-cysteine-assisted method for the growth of MoS₂ nanosheets on carbon nanotubes for high-performance lithium ion batteries 
Seung-Keun Park ,  Seung-Ho Yu ,  Seunghee Woo ,  Bo Quan ,  Dong-Chan Lee ,  Min Kun Kim ,  Yung-Eun Sung and Yuanzhe Piao  
Dalton Trans., 2013,42, 2399-2405 DOI: 10.1039/C2DT32137H  

Bioinorganic chemistry 
Emma Raven ,  Nicholas E. Le Brun ,  Jonathan McMaster ,  Jan Reedijk and Nigel J. Robinson  
Dalton Trans., 2013,42, 3027-3028 DOI: 10.1039/C2DT90214A  

Biomimetic model for [FeFe]-hydrogenase: asymmetrically disubstituted diiron complex with a redox-active 2,2′-bipyridyl ligand 
Souvik Roy ,  Thomas L. Groy and Anne K. Jones  
Dalton Trans., 2013,42, 3843-3853 DOI: 10.1039/C2DT32457A  

A polar tetrazolyl-carboxyl microporous Zn(II)–MOF: sorption and luminescent properties 
Lei Hou ,  Li-Na Jia ,  Wen-Juan Shi ,  Yao-Yu Wang ,  Bo Liu and Qi-Zhen Shi  
Dalton Trans., 2013,42, 3653-3659 DOI: 10.1039/C2DT31968C  

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., 2013,42, 1333-1337 DOI: 10.1039/C2DT31698F  

Pt–Ag clusters and their neutral mononuclear Pt(II) starting complexes: structural and luminescence studies 
Juan Forniés ,  Violeta Sicilia ,  José M Casas ,  Antonio Martín ,  José A. López ,  Carmen Larraz ,  Pilar Borja and Carmen Ovejero  
Dalton Trans., 2011,40, 2898-2912 DOI: 10.1039/C0DT01451F  

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

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N-heterocyclic carbenes are neutral σ donors and electron rich, making them attractive for use as ligands in transition metal catalysts. By changing the nature of the azole ring (nitrogen heterocycle containing at least one other atom of S, N or O) and the substituents, the electronic and steric properties can be modified.

X-Ray structure of a 6-membered N-heterocylic carbene complex of palladium

Studies of expanded NHCs containing a 6- or 7-membered ring have only recently started to appear in the literature. This includes that of Nechaev and colleagues who have synthesized a series of new 6- and 7-membered NHC palladium complexes. Kolychev and Nechaev screened the complexes as catalysts for Suzuki-Miyaura cross-coupling of heteroaryl chlorides and bromides. They tested the catalysts using ‘green‘ reaction conditions and showed that reaction products are clean with no homo coupling products formed.

These systems are very attractive – it will be exciting to see how expanded ring NHCs are utilized more in the future…

Download the full Dalton Transactions paper to find out more:

Expanded Ring Diaminocarbene Palladium Complexes: Synthesis, Structure, and Suzuki–Miyaura Cross-Coupling of Heteroaryl Chlorides in Water
Eugene Kolychev and Mikhail Nechaev
Dalton Trans., 2013, DOI: 10.1039/C3DT32860K

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

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:

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