Dalton Transactions Blog

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

John Stride from the University of New South Wales, Sydney and colleagues have prepared a copper-based metal–organic framework that demonstrates gas selective adsorption of hydrogen over nitrogen.

The microporous framework has potential application in the isolation of hydrogen from nitrogen in ammonia sythesis waste streams.

Read more in this Dalton Transactions Hot article available FREE until 11th April 2011:

A flexible copper based microporous metal–organic framework displaying selective adsorption of hydrogen over nitrogen
Muhammad Arif Nadeem, Aaron W. Thornton, Matthew R. Hill and John Arron Stride
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C0DT01531H, Hot Article

In this Dalton Transactions Hot Article, chemists from Australia and the US have studied the solution behaviour of two novel platinum-based antitumour complexes.

The dinuclear, polyamine-linked complexes show significant cytotoxicity and antitumour activity compared to other polynuclear platinum complexes.

The rate constants for hydrolysis of the two complexes and the acid dissociation constants of the aquated aqua ligands of their aquated derivatives are reported. The values are of interest because the aquated species are more reactive than their hydroxo counterparts in the context of DNA binding.

Read more for FREE until 12th April 2011:
Solution studies of dinuclear polyamine-linked platinum-based antitumour complexes
Rasha A. Ruhayel, Ibrahim Zgani, Susan J. Berners-Price and Nicholas P. Farrell
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT00001B, Paper

In this Dalton Transactions Hot article, two new Co^_II/Ln^III complexes are synthesized with 2-amino-isobutyric acid.

The complexes are hetero-heptametallic clusters ( [Co^II₆Ln^III] )with 2-amino-isobutyric acid as the ligand, forming 3d-4f metallic cages in which the Ln^III centre (Ln = Eu, Dy) is encapsulated within a Co^II₆ trigonal prism.

Constantinos J. Milios and co-workers from the University of Crete looked at the optical and magnetic properties of their complexes, and found that one (containing Dysprosium) has the potential to be a single molecule magnet, while the other (containing Europium) exhibited luminescent properties.

Read the full article to find out more about these 3d-4f metallic cages…

Unique trigonal prism encapsulated Ln complexes: a [CoII6Eu] and a [CoII6Dy] cage
Maria Orfanoudaki, Ioannis Tamiolakis, Milosz Siczek, Tadeusz Lis, Gerasimos S. Armatas, Spiros A. Pergantis and Constantinos J. Milios
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10052A, Communication

FREE TO READ until 12th April

In this new Dalton Transactions Hot Article, Macgregor, Welch, Zanello et al. report the synthesis of carboranes substituted with a range of ArF substituents.  The team also describe the results of spectroscopic, computational and (spectro)electrochemical studies for identifying the best ArF substituent to stabilise the new carboranes once reduced.

Supraicosahedral heteroborane chemistry is an area of contemporary interest. Heteroborane clusters with >12 vertices can be challenging to synthesise and can present interesting problems for computational chemists.

Supraicosahedral heteroborane chemistry is important as  such compounds could find valuable applications in a wide range of fields  from bond activation and homogeneous catalysis to medicine.

Read for free until the 1st April 2011 here.

Spectroscopic, structural, computational and (spectro)electrochemical studies of icosahedral carboranes bearing fluorinated aryl groups
Hugo Tricas, Marta Colon, David Ellis, Stuart A. Macgregor, David McKay, Georgina M. Rosair, Alan J. Welch, Ivan V. Glukhov, Fulvio Rossi, Franco Laschi and Piero Zanello
Dalton Trans., 2011, Advance Article, DOI: 10.1039/C0DT01798A