Archive for the ‘Hot Articles’ Category

Hot Article: Very Vanadium

Phalguni Chaudhuri and colleagues, from the Max-Planck-Institut in Mulheim, Germany, investigate the interactions between a potentially tetradentate tripodal ligand and the biologically important metal, Vanadium. What were the resulting complexes? Find out in  their Hot Article – FREE to read until mid November.

Non-oxo 5-coordinate and 6-coordinate vanadium(IV) complexes with their precursor [LVIII(CH3OH)]0, where L = a trianionic aminetris(phenolate)-[N,O,O,O] donor ligand: a magnetostructural and EPR study
Takashi Kajiwara, Rita Wagner, Eckhard Bill, Thomas Weyhermüller and Phalguni Chaudhuri
Dalton Trans., 2011, DOI: 10.1039/C1DT11277E

 

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Hot Article: Chirality effects on star-burst complexes

In their Dalton Trans. Hot Article, a group of Japanese chemists led by Hisako Sato, used vibrational circular dichroism (VCD) spectroscopy to study the stereochemical properties of a star-burst type tetranuclear Ru(III) complex. By comparing the VCD spectra of eight diastereomeric enantiomers, they were able to see the homo- or hetero-chiral nature of the bridging part of the compound which connected the central core and the peripheral region

Chirality effects on core-periphery connection in a star-burst type tetranuclear Ru(III) complex: application of vibrational circular dichroism spectroscopy
Hisako Sato, Fumi Sato, Masahiro Taniguchi and Akihiko Yamagishi
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C1DT11510C

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HOT Article: Forbidden compositions?

This HOT article by Mukherjee et al. reports the synthesis, structure, magnetic properties and DFT studies of four Cu(II)-azide polymers. Cu(II)-azide polymers are presently  being studied by many groups due to their interesting structural variation and magnetic properties. In this paper, three out of the four compounds studied are of new structural topologies.  All four complexes exhibit an overall ferromagnetic behaviour; the magnetic results are corroborated by DFT studies. The structural analysis shows how a simple change in the structure of the blocking ligand can generate entirely different structures and magnetic properties, even though the basic structures seems to be almost identical. It is also shown that another blocking diamine does not produce similar complexes under the same reaction conditions, which leads to the question: are certain compositions forbidden?

Read more about forbidden compositions and magnetic behaviour for FREE until the 2nd November at:
CuII-azide polymers with various molar equivalents of blocking diamine ligands: synthesis, structures, magnetic properties with DFT studies
Sandip Mukherjee, Yogesh P. Patil and Partha Sarathi Mukherjee
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT11312G

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Hot Article: Using DFT to understand the heme active site of P450

Frank Neese (Max Planck) and Serena DeBeer (Cornell University), predict iron K-edge XAS pre-edge features for iron complexes using time-dependent density functional theory in this Dalton Transactions Hot article.

This work is building on the teams earlier investigations into ferrous and ferric complexes. The group will use their improved understanding of high valent iron intermediates to explain more about the behaviour of metalloproteins, and in this case they look at the heme active site of P450.

This paper is part of a themed issue guest edited by Stuart MacGregor (Heriot-Watt) on Computational Chemistry of Molecular Inorganic Systems that will be published online in the next few weeks. Make sure you hear about it by signing up to the Dalton Transactions table of contents e-alerts.

Read the full article for FREE  until 8th November to find out more about the use of X-ray absorption spectroscopy to understand metalloproteins…

Prediction of high-valent iron K-edge absorption spectra by time-dependent Density Functional Theory
P. Chandrasekaran, S. Chantal E. Stieber, Terrence J. Collins, Lawrence Que, Jr., Frank Neese and Serena DeBeer
Dalton Trans., 2011, DOI: 10.1039/C1DT11331C

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HOT Article: A new structural type in Mn chemistry

In this HOT article, Constantinos J. Milios and co-workers describe the synthesis, crystal structures and magnetic properties of (a hexanuclear and an octanuclear) manganese(III) complexes based on a new oxime ligand, 2-dihydroxy-2-phenylacetamidine.  This is the first time that this ligand has been  used for the synthesis of polynuclear complexes of any transition metal ion. Even though the hexanuclear complex resembles the previously reported [Mn6] clusters with salicyl-based oximes, the octanuclear complex presents a new structural type in Mn chemistry. Both complexes display moderate spin ground states (S = 3). The authors believe this new ligand is a promising candidate for a new extended family of manganese complexes with interesting magnetic properties and as impressive structures as its parent salicyl- or pyridyl-based oxime ligands.

Read more about this new ligand and potential magnetic properties for FREE until 25 th October at:

A new oxime ligand in manganese chemistry: a [Mn8] and a [Mn6] cage from the use of 2-dihydroxy-2-phenylacetamidine
Andreas G. Flamourakis, Demetrios Tzimopoulos, Milosz Siczek, Tadeusz Lis, James R. O’Brien, Pericles D. Akrivos and Constantinos J. Milios
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT11455G

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Hot Article: Organoruthenium anti-cancer complexes

Peter Sadler from Warwick University, and collaborators at the Chinese Academy of Sciences have developed a ruthenium arene anticancer complex that inhibits the action of protein tyrosine phosphatase 1B, which regulates insulin levels.

In this Dalton Transactions Hot article the team investigate how the complex interacts with the active site of PTP1B by using a similiar shaped molecule as a model. Their compound was found to have an IC50 of 19 μM.

Read the full article for FREE until 2nd November to find out more about how this anticancer compound works…

Reactions of an organoruthenium anticancer complex with 2-mercaptobenzanilide—a model for the active-site cysteine of protein tyrosine phosphatase 1B
Yumiao Han, Qun Luo, Xiang Hao, Xianchan Li, Fuyi Wang, Wenbing Hu, Kui Wu, Shuang Lü and Peter J. Sadler
Dalton Trans., 2011, DOI: 10.1039/C1DT11189B

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Unusual structure is ‘silver’ lining in Ag study

A team of scientists from Poland have been playing around with silver-pyrazine complexes and made an unusual crystal structure of a Ag(I) by–product in the process. Piotr J. Leszczyński, Wojciech Grochala and colleagues from Warsaw studied the decomposition of di(pyrazine)silver(II) peroxydisulfate under various heat and chemical processes.

Much work has been carried out on the copper analogue before this but only now is the silver version really being looked at. Read more in this recent Hot Article – FREE to read until the end of October:

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Thermal and chemical decomposition of di(pyrazine)silver(II) peroxydisulfate and unusual crystal structure of a Ag(I) by-product
Piotr J. Leszczyński, Armand Budzianowski, Łukasz Dobrzycki, Michał K. Cyrański, Mariana Derzsi and Wojciech Grochala
Dalton Trans., 2011, DOI: 10.1039/C1DT10744E

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HOT Article: Accidentally on purpose, a relatively simple model to study magneto-structural relationships in complex Mn clusters

In this HOT Article, the serendipitous self-assembly of the complex [MnIII2ZnII2(Ph-sao)2(Ph-saoH)4(hmp)2], whose magnetic core consists solely of two symmetry equivalent Mn(III) ions linked by two symmetry equivalent –N–O– moieties, provided Brechin and co-workers with a relatively simple model complex with which to study the magneto-structural relationships in more complicated polynuclear oxime-bridged Mn(III) cluster compounds.

Read more for FREE until 21st September at:

Accidentally on purpose: construction of a ferromagnetic, oxime-based [MnIII2] dimer
Ross Inglis, Edel Houton, Junjie Liu, Alessandro Prescimone, Joan Cano, Stergios Piligkos, Stephen Hill, Leigh F. Jones and Euan K. Brechin
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT11118C
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HOT Article: Coordination scales

In this HOT article, Díaz-Torres and Alvarez have developed a scale which attempts to quantify the weakly coordinating character of a variety of solvents and anions towards a transition metal or a lanthanide.  This was made possible by analyzing crystal structures for the presence of coordinated and uncoordinated groups (solvents or anions) in the presence of a transition metal or a lanthanide and extracting from this coordinating ability indices. These indices should prove very useful in providing general trends  allowing comparison between different solvents or anions and should be very useful for the broad organometallic community.

Read more for FREE until 11th October about this elegant solution:

Coordinating ability of anions and solvents towards transition metals and lanthanides
Raúl Díaz-Torres and Santiago Alvarez
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT11000D

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HOT Article: 1-borabenzonitrile

In this HOT article, Cade and Hill describe the synthesis of a salt of the 1-borabenzonitrile anion as its tetrabutylammonium salt and a preliminary exploration of its coordination chemistry in which it behaves as neither a conventional nitrile nor an isonitrile. The authors present computational, spectroscopic and crystallographic evidence for the heterocycle and a ruthenium complex containing the anion as an “arene” ligand.

Read more for FREE until the 4th October at:
1-Borabenzonitrile (B-cyanoboratabenzene)
Ian A. Cade and Anthony F. Hill
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10849B

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