Dalton Transactions Blog

In this HOT article, a very careful synthetic and catalytic study of the use of di- and trisulfonated phosphines with o, m and o, m, m substitution patterns is described. Pd complexes of these were tested for  copolymerizations with polar monomers. This led to a novel anionic phosphine sulphonate Pd(II)-based pre-catalyst salt for polymerisation reactions.  Although, polymerisation in the presence of methyl acrylate, acrylonitrile and vinyl acetate led to reduced incorporation values compared to the available literature reports in combination with problems that are attributed to aggregation of the catalyst in most cases, the facile synthesis of chelating highly polar ligands which show high water solubility could be of significant interest for homogeneous catalysis by application in other systems.

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Synthesis of non-symmetrically sulphonated phosphine sulphonate based Pd(II) catalyst salts for olefin polymerisation reactions
Timo M. J. Anselment, Carly E. Anderson, Bernhard Rieger, M. Bele Boeddinghaus and Thomas F. Fässler
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10372E

In this Dalton Transactions Hot Article, Maria-Angels Carvajal and colleagues probe the photomagnetic properties of a copper octacyanomolybdate complex using high level ab initio calculations.

The authors describe in detail the photomagnetic process arising from a local Mo d-d excitation in the complex. They also show that there is a small energy barrier for the reverse reaction and that it can be induced by light. They also investigate the temperature dependence of the magnetic susceptibility and compare it with experimental values.

Photomagnetic materials are of interest as candidates for use in memory devices and optical switches.

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Insights on the photomagnetism in copper octacyanomolybdates
Maria-Angels Carvajal, Rosa Caballol and Coen de Graaf
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10120J, Paper

In this Dalton Transactions Hot Article, Graham Bowmaker from the University of Auckland and colleagues, synthesised three new disilver(I) carbonate/tertiary phosphine complexes.

Solution and mechanochemical methods were used. The use of the mechanochemical synthesis demonstrates an additional aspect of this type of method. The study also demonstrates the value of ATR IR and CPMAS NMR for monitoring the progress of mechanochemical synthesis.

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Solution and mechanochemical syntheses, and spectroscopic and structural studies in the silver(I) (bi-)carbonate: triphenylphosphine system
Graham A. Bowmaker, Effendy, John V. Hanna, Peter C. Healy, Scott P. King, Claudio Pettinari, Brian W. Skelton and Allan H. White
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10416K, Paper

In this HOT article, the authors have extended their work in understanding enantioselective catalysis by coordination compounds. The role of steric hindrance in controlling the binding mode of propylene oxide to a novel vanadyl salen-type complex N,N‘-bis(5-tert-butylsalicylidene)-1,2-cyclohexanediamino-vanadium(IV) oxide, [VO(3)], has been investigated using CW/pulse EPR, ENDOR and HYSCORE spectroscopy and compared to that of the parent complex N,N‘-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamino-vanadium(IV) oxide, [VO(1)]. Removal of the ‘inner tert-butyl groups from the salicylidene rings reduces the steric hindrance between the ligand and epoxide substrate. As a result the selectivity for binding single enantiomers of propylene oxide in these complexes is reversed in [VO(3)] relative to [VO(1)].

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Structure and pulsed EPR characterization of N,N‘-bis(5-tert-butylsalicylidene)-1,2-cyclohexanediamino-vanadium(IV) oxide and its adducts with propylene oxide
E. Carter, I. A. Fallis, B. M. Kariuki, I. R. Morgan, D. M. Murphy, T. Tatchell, S. Van Doorslaer and E. Vinck
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10378D

In this HOT article, the molecular structures of 1,2-closo-P₂B₁₀H₁₀ (1) and 1,2-closo-As₂B₁₀H₁₀ (2) have been determined by gas electron diffraction and the results obtained compared with those from computation at the MP2/6-31G** level of theory. The first examples of metalladiphosphaboranes and a considerable extension of the range of known metalladiarsaboranes, these compounds being prepared from deboronated derivatives of 1 and 2, respectively, are also reported.

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New chemistry of 1,2-closo-P₂B₁₀H₁₀ and 1,2-closo-As₂B₁₀H₁₀; in silico and gas electron diffraction structures, and new metalladiphospha- and metalladiarsaboranes
R. McLellan, N. M. Boag, K. Dodds, D. Ellis, S. A. Macgregor, D. McKay, S. L. Masters, R. Noble-Eddy, N. P. Platt, D. W. H. Rankin, H. E. Robertson, G. M. Rosair and A. J. Welch
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10540J

A N^N Pt(II) bis(acetylide) complex containing coumarin was prepared in this Dalton Transactions Hot article.

The coordination chemistry of the complex was investigated to better understand its phosphorescence. Room temperature phosphorescence of coumarin has not previously been observed at room temperature, which is an exciting discovery.

The authors went on to use their complex as a sensitizer for triplet–triplet-annihilation based upconversion and luminescent oxygen sensing, with encouraging results.

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Coumarin phosphorescence observed with NN Pt(II) bisacetylide complex and its applications for luminescent oxygen sensing and triplet–triplet-annihilation based upconversion
Haiyang Sun, Huimin Guo, Wenting Wu, Xin Liu and Jianzhang Zhao
Dalton Trans., 2011, DOI: 10.1039/C1DT10490J

The most stable crystal structures of different TCN compounds are investigated in this Dalton Transactions Hot article.

Philippe F. Weck and colleagues from the University of Nevada-Las Vegas, USA, use gradient-corrected density functional theory to look at the structures and properties of technetium nitride phases.

Technetium nitride is used in nuclear waste management, as nitride forms are a good way of storing technetium isotopes, a common by product of the nuclear fuel cycle, and also in nuclear medicine, where it acts a a radiopharmaceutical (if you are interested in radiopharmaceuticals, check out our recent themed issue)

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Interplay between structure, stoichiometry and properties of technetium nitrides
Philippe F. Weck, Eunja Kim and Kenneth R. Czerwinski
Dalton Trans., 2011, DOI: 10.1039/C1DT10334B

Rechargeable lithium-ion batteries (LIBs) have successfully dominated the commercial power supply market for advanced portable electronics.  In this regard, metallic Sn has attracted a great deal of interest as an anode material because of its high theoretical capacity offering a significant advantage over the currently used graphite but until now has not been utilized due to the huge volumetric changes during Li-insertion/extraction cycling, which leads to rapid pulverization and poor cyclability of the materials. 

This HOT article reports an interesting study on Sn/PPy composite as negative electrode using carboxymethyl cellulose (CMC) binder for Li-ion batteries.   The electrochemical results show that both the capacity retention and the rate capability are in the same order of nano-Sn/PPy-CMC > nano-Sn/PPy-PVDF > nano-Sn-CMC > nano-Sn-PVDF. Scanning electronic microscopy (SEM) and electrochemical impedance spectroscopy (EIS) results show that CMC can prevent the formation of cracks in electrodes caused by the big volume changes during the charge–discharge process, and the PPy in the composite can provide a conducting matrix and alleviate the agglomeration of Sn nanoparticles. The present results indicate that the nano-Sn/PPy composite could be suitable for the next generation of anode materials.

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Tin/polypyrrole composite anode using sodium carboxymethyl cellulose binder for lithium-ion batteries
Shu-Lei Chou, Xuan-Wen Gao, Jia-Zhao Wang, David Wexler, Zhao-Xiang Wang, Li-Quan Chen and Hua-Kun Liu
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10396B