Dalton Transactions Blog

This HOT article describes the synthesis and crystal structures of four mono- or bi-cyclic Mo/S/Cu clusters from a pre-designed cluster [(η⁵-C₅Me₅)₂Mo₂(µ₃-S)₄(CuMeCN)₂]²⁺ with tetraphosphine or N,P mixed ligands.  The femtosecond third order non-linear optical (NLO) performances of the products are enhanced due to the increased number of cluster cores.  As both the cluster-based building blocks and the multiple organic linkers are pre-designed, it could be useful for the rational design and assembly of coordination frameworks, possibly allowing the preparation of other new materials with enhanced NLO performance.

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Assembly of bicyclic or monocyclic clusters from [(η⁵-C₅Me₅)₂Mo₂(µ₃-S)₄(CuMeCN)₂]²⁺ with tetraphosphine or N,P mixed ligands: syntheses, structures and enhanced third-order NLO performances
Zhi-Gang Ren, Sha Sun, Min Dai, Hui-Fang Wang, Chun-Ning Lü, Jian-Ping Lang and Zhen-Rong Sun
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10685F

In this HOT article, Harder and Spielmann describe some alkaline earth metal aminoborane ligands and their thermal behaviour.  By using their new ditopic bis(ketiminate) ligands, they have been able to synthesize binuclear complexes that are pre-organised for constructing bridging aminoborane oligomers as ligands. By heating the initial non-bridging complexes, the aminoboranes couple and lose H₂. The loss of hydrogen from aminoborane ligands has practical relevance to hydrogen storage chemistry and also to the fields of solid state and metal-organic chemistry.

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Binuclear magnesium amidoborane complexes: characterization of a trinuclear thermal decomposition product
Jan Spielmann and Sjoerd Harder
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10694E

Jingping Wang and colleagues make the first examples of isopolyoxotungstates-supported carbonyl metal compounds. Read more about there three novel octatungstate-supported tricarbonyl metal derivatives in their CrystEngComm Hot Article – free for you to read until the 25 August 2011.

Novel octatungstate-supported tricarbonyl metal derivatives: {[H₂W₈O₃₀][M(CO)₃]₂}⁸⁻ (M = MnI and ReI)
Jingyang Niu, Linping Yang, Junwei Zhao, Pengtao Ma and Jingping Wang
Dalton Trans., 2011, DOI: 10.1039/C1DT11042J

In this HOT article,  Fornies and co-workers describe the efficient stereoselective synthesis of salts of any of the following trifluoromethylplatinum(IV) isomeric couples: cis-/trans-[Pt(CF₃)₄Cl₂]^2- and fac-/mer-[Pt(CF₃)₃Cl₃]^2-. All these compounds can be isolated in high yields and have been characterised by a combination of analytical, spectroscopic and X-ray diffraction methods.

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Efficient and stereoselective syntheses of isomeric trifluoromethyl-platinum(IV) chlorides
Sonia Martínez-Salvador, Pablo J. Alonso, Juan Forniés, Antonio Martín and Babil Menjón
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10557D

In this Dalton Transactions Hot article Yu Gong and Lester Andrews from the University of Virgina, USA, look at  how laser-ablated thorium and uranium react with dimethyl ether molecules.

Uranium and thorium can activate chemical bonds, making them useful in catalysis, and here Gong and Andrews use density functional theory and matrix infrared spectroscopy to understand what types of reaction products can be obtained under different conditions.

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Matrix infrared spectroscopic and density functional theoretical investigations on thorium and uranium atom reactions with dimethyl ether
Yu Gong and Lester Andrews
Dalton Trans., 2011, DOI: 10.1039/C1DT10725A

In this Dalton Transactions Hot Article, Cameron Jones and colleagues from Monash University, Australia prepared a series of extremely bulky secondary amines.

Deprotonation of the amines with LiBuⁿ NaH or KH resulted in alkali metal amide complexes. Reaction of the amides with germanium, tin or lead chloride yielded the first two-coordinate monomeric amido germanium(II) and tin(II) chloride complexes and a chloride bridged amido-lead(II) dimer.

These compounds hold potential as precursors for kinetically stabilised low oxidation state and/or low coordination number main group complexes.

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Extremely bulky amido-group 14 element chloride complexes: Potential synthons for low oxidation state main group chemistry
Jiaye Li, Andreas Stasch, Christian Schenk and Cameron Jones
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10678C, Paper

In this Dalton Transactions Hot Article, Tristram Chivers and colleagues from the University of Calgary have reported several new thallium and indium complexes of multidentate chalcogen-centred PCP-bridged ligands.

The binuclear mixed-valent Tl(I)/Tl(III) complex with ligand [(Se)C(PPh₂Se)₂]^2- exhibits a one-dimensional polymeric structure while in the polycyclic Tl(I)/Tl(I) complexes with [(SPh₂P)₂CE′E′C(PPh₂S)₂]^2-  (E′ = S, SE) the dimeric ligands remain intact.

Three heteroleptic In complexes were obtained by reaction of InCl₃ with [Li(TMEDA)][HC(PPh₂Se)₂], [Li(TMEDA)]₂[(E′)C(PPh₂E)₂] or [Li(TMEDA)]₂[(E′)C(PPh₂E)₂] (E = S, E′ = S, SE).

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Homoleptic, heteroleptic and mixed-valent thallium and indium complexes of multidentate chalcogen-centred PCP-bridged ligands
Maarit Risto, Tristram Chivers and Jari Konu
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10646E, Paper

This Dalton Transactions Hot article investigates the intermolecular hydroamination of heteroatom-substituted allenes.

The addition of hydrogen-nitrogen bonds to carbon multiple bonds is an important reaction in organic synthesis, and here Laurel Schafter and Rashidat Oyinla from the University of British Columbia in Canada, use a transition metal catalyst to create five-membered N,O-chelating complexes.

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Intermolecular hydroamination of oxygen-substituted allenes. New routes for the synthesis of N,O-chelated zirconium and titanium amido complexes
Rashidat O. Ayinla and Laurel L. Schafer
Dalton Trans., 2011, DOI: 10.1039/C1DT10448A

In this HOT article, Ribas and co-workers build on previous studies on the mechanism of Ullmann cross coupling reactions using a well-defined aryl-copper(III) complex. Fundamental mechanistic knowledge of these couplings is still scarce but is gaining renewed interest due to the cost and toxicity benefits in comparison to Pd-based methodologies for the synthesis of key intermediates in the pharmaceutical industry. The reactivity of well defined aryl–Cu^III species in front of phenol-type nucleophiles was found to differ substantially from the reactivity with corresponding phenolates, and a significant enhancement was found to produce the same aryl–O coupling product. Mechanistic studies showed that easy deprotonation of coordinated secondary amines was responsible for the intense LMCT band at 545 nm; indeed, this pH-dependent reactivity of the pincer-like coordinated ligand somewhat enhanced its reactivity.

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Aryl–O reductive elimination from reaction of well-defined aryl–Cu^III species with phenolates: the importance of ligand reactivity
Alicia Casitas, Nikolaos Ioannidis, George Mitrikas, Miquel Costas and Xavi Ribas
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10428D