Dalton Transactions Blog

Christopher F. Blanford’s group from the University of Oxford have solved the x-ray structure for bilirubin oxidase from the plant pathogen Myrothecium verrucaria. This enzyme efficiently catalyses the oxidation of bilirubin to biliverdin, and can be used in O₂ reduction.

The authors look at the environment of the copper in the enzyme, to better understand and improve its stability  when is attached to the carbon surface of a pyrolytic graphite electrode. When attached to an electrode it can act as a cathode catalyst, and this enhanced electrocatalytic response of the material is an important step in developing viable low-temperature bio-fuel cells.

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Bilirubin oxidase from Myrothecium verrucaria: X-ray determination of the complete crystal structure and a rational surface modification for enhanced electrocatalytic O2 reduction
James A. Cracknell, Thomas P. McNamara, Edward D. Lowe and Christopher F. Blanford
Dalton Trans., 2011, DOI: 10.1039/C0DT01403F

This Dalton Transactions Hot article explores metalloligands inspired by the active site of enzymes.

Marcetta Y. Darensbourg and colleagues from Texas A& M University, look at NiFe-heterobimetallic complexes, and their bonding and structure, to increase their understanding of the features of natural bimetallic sites in enzymes.

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cis-Dithiolatonickel as metalloligand to dinitrosyl iron units: the di-metallic structure of Ni(μ-SR)[Fe(NO)2] and an unexpected, abbreviated metalloadamantyl cluster, Ni2(μ-SR)4[Fe(NO)2]3
Chung-Hung Hsieh, Rachel B. Chupik, Scott M. Brothers, Michael B. Hall and Marcetta Y. Darensbourg
Dalton Trans., 2011, DOI: 10.1039/C1DT10438A

In this Dalton Transactions Hot article, Yongge Wei, Yuan Wang and colleagues from Peking University and Tsinghua University make three rigid-rod conjugated organic-hexamolybdate hybrids, a type of organic-polyoxometalate or Lindqvist ion.

Polyoxometalates have potential for use in medicine for anti-tumour and anti-viral applications, and their unusual properties make them useful in catalysis and potentially in the electonics industry.

In this work the organic-polyoxometalates have different amino groups at the terminus, which allows the fabrication of more complicated polyoxometalate (POM) hybrid materials. The amino groups can have different rod lengths and substituents allowing tuning of the materials properties.

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Monosubstituted arylimido hexamolybdates containing pendant amino groups: synthesis and structural characterization
Yi Zhu, Zicheng Xiao, Longsheng Wang, Panchao Yin, Jian Hao, Yongge Wei and Yuan Wang
Dalton Trans., 2011, DOI: 10.1039/C1DT10168D

This Dalton Transactions Hot article looks at the self assembly of polyhedral cages.

This builds on the authors previous work looking at coordination cages based on simple bis-bidentate bridging ligands with transition metal dications. In this paper they use new ligands with central thiophene or furan spacers, which affect the structure of the cages formed, and so the properties of these compounds.

Read the full article to find out more about these coordination cages…

Molecular squares, cubes and chains from self-assembly of bis-bidentate bridging ligands with transition metal dications
Andrew Stephenson and Michael D. Ward
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10263J, Paper

In this Dalton Transactions Hot article, Herbert W. Roesky and Dietmar Stalke and collegues from
Universitat Gottingen, Germany, make a stable silicon(II) monohydride and examine its electronic structure.

Group 14 hydrides are used in synthetic chemistry, and as precursors to make alloys, such as amorphous silicon, that are used in  electronic devices. For this reason the ability to make stable compounds is very desirable, and an understanding of their structure will help develop the field of silicon chemistry.

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A stable silicon(II) monohydride
Anukul Jana, Dirk Leusser, Ina Objartel, Herbert W. Roesky and Dietmar Stalke
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C0DT01675F, Paper

FREE TO READ until 6th May

In this Dalton Transactions Hot article by William T. Eckenhoff and Tomislav Pintauer, Duquesne University, Pittsburgh, USA, copper(II) complexes with the Me₆TREN ligand and AIBN were used as atom transfer radical addition catalysts.

Atom transfer radical addition is a way of making carbon-carbon bonds using a transition metal catalyst. This method can require a large ratio of catalyst to get a good yield, and can be difficult to recycle, so new ways to optimise this system are crucial.

Here the authors use a free radical diazo initiator (AIBN) to regenerate the catalyst in situ, and use the Me₆TREN ligand to reduce the amount of copper in a higher oxidation state, which would otherwise deactivate the catalyst. This makes for a much more efficient reaction, and here this system was used to catalyze the addition of CCl₄, CHCl₃, CBr₄, and CHBr₃ to a series of alkenes.

Read the full article to find out more about this method for controlled radical addition…

Atom transfer radical addition (ATRA) catalyzed by copper complexes with tris[2-(dimethylamino)ethyl]amine (Me6TREN) ligand in the presence of free-radical diazo initiator AIBN
William T. Eckenhoff and Tomislav Pintauer
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10189G, Paper

FREE TO READ until 21st April