Author Archive

Dalton Transactions: issue 47

Discover the beautiful outside cover of Dalton Transactions issue 47.  The  authors would like to gratefully acknowledge Mrs. Kshitija Kolvankar for the design of the cover page highlighting the work of Serrano and co-workers  in developing a simple and novel synthetic route towards solvate analogous of classical solvate precursors.  It involves stirring Pd3(AcO)6 in the solvent of choice, in the stoichiometric presence of protic ligands. The examples presented with imidate ligands allowed the preparation of acetonitrile, dimethylsulfoxide and dimetylsulfide bis-imidate complexes.  The possibility of extending the route presented to other combinations of solvents/protic electrophiles makes it a potentially useful synthetic tool, and also promising applications in catalysis could be expected for the new precursor and its derivatives.

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Bis(imidate)palladium(II) complexes with labile ligands. Mimics of classical precursors?
Gregorio Sánchez, Joaquín García, Marina Martínez, Anant R. Kapdi, José Pérez, Luis García and J. Luis Serrano
Dalton Trans., 2011, 40, 12676-12689
DOI: 10.1039/C1DT10426H

The inside front cover highlights research from Huang et al.

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A new photocatalyst: Bi2TiO4F2 nanoflakes synthesized by a hydrothermal method
Shaoying Wang, Baibiao Huang, Zeyan Wang, Yuanyuan Liu, Wei Wei, Xiaoyan Qin, Xiaoyang Zhang and Ying Dai
Dalton Trans., 2011, 40, 12670-12675
DOI: 10.1039/C1DT10889A

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Ligand duality in Oxygen Atom Transfer

The dual nature of donor ligands is explored in Oxygen Atom Transfer (OAT) in this hot article by Adam Veige and co-workers.  In this study, donor ligands enhance the rate of OAT by hindering µ-O dimer formation; however, the addition of a too strongly coordinating ligand can actually prevent OAT by
making the transfer thermodynamically unfavorable.

Read more about this ligand duality for FREE until 13th December 2012:

The influence of reversible trianionic pincer OCO3– µ-oxo CrIV dimer formation ([CrIV]2(µ-O)) and donor ligands in oxygen-atom-transfer (OAT)
Matthew E. O’Reilly, Trevor J. Del Castillo, Khalil A. Abboud and Adam S. Veige
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C1DT11104C

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HOT Article: Fine tuning of catalyst performance

Transition metal complexes bearing functional P,N-type ligands attract much attention because they combine hard nitrogen donor(s) and soft phosphorus donor(s) and offer considerable chemical and structural diversity. In this HOT Article,  Braunstein et al. report several palladium/cobalt and nickel complexes with phosphino-oxazoline ligands. Some of the nickel complexes were further checked for their ethylene reactivity, and showed activity for ethylene non-selective oligomerization. Interestingly, a reversible interconversion transform phenomena was observed between a couple of the isomeric Ni-complexes with variation of the solvent between CH2Cl2 and CHCl3.
The role of functional bidentate ligands in catalysis provides a versatile tool for fine tuning the performance of catalysts (Lewis base – Lewis acid interactions).

Read more for FREE until 29th November at:
A phosphino-oxazoline ligand as a P,N-bridge in palladium/cobalt or P,N-chelate in nickel complexes: catalytic ethylene oligomerization
Shuanming Zhang, Roberto Pattacini, Suyun Jie and Pierre Braunstein
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT11352F

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HOT Article: Figures of eight

Braunstein and co-workers have formed a dinuclear Ir(I) complex with a bis-NHC ligand in situ from
1,1′-((4,6-dimethyl-1,3-phenylene)bis(methylene))bis(3-methyl-1H-imidazol-3-ium) in
the presence of Cs2CO3 and [Ir(µ-Cl)(cod)]2. Its solid-state structure, determined by X-ray
diffraction, shows a figure-of-eight loop with both the P and M enantiomers being present. Solution NMR studies were also performed to examine the enantiodiscrimination between them.

Read more for FREE until the 29th November 2011 at:

Chiral anion-based NMR enantiodiscrimination of a dinuclear, cationic Ir(I) NHC complex with a figure-of-eight loop structure
Xianghao Liu, Jérôme Lacour and Pierre Braunstein
Dalton Trans., 2012, Advance Article
DOI: 10.1039/C1DT11604E

Also read about the formation of unprecedented eight-membered chelates at:

Contrasting bonding modes of a tridentate bis(oxazoline)phosphine ligand in cobalt and iron vs. palladium complexes: unprecedented N,N-coordination for a N,P,N ligand
Anthony Kermagoret and Pierre Braunstein
Dalton Trans., 2008, 585-587
DOI: 10.1039/B717021C

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HOT Article: Ionic liquids in biphasic catalysis

Oelkers and Sundermeyer, in this HOT Article, present a general approach towards 1,4-diazabutadiene (DADS) ligands with various onium cations via acid–base reactions and towards their noble-metal complexes. The solubility and immobilization of such complexes in ILs is quantitatively shown via photometric measurements using a chromophoric Mo(0) DADS complex in a toluene/[BMIM]OTf biphasic mixture as a model system. It was shown that complexes with ionic liquid (IL) – typical onium salts of sulfonated diazadienes as ligands are strongly retained in an IL phase in contact with a toluene phase, which may make these ligands potentially useful in IL/organic biphasic catalysis.

Read more for FREE until mid-November:

Sulfonate-tagged 1,4-diazabutadiene (DADS) ligands and their noble-metal complexes – synthesis, characterization and immobilization in ionic liquids
Benjamin Oelkers and Jörg Sundermeyer
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT10939A

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HOT Article: True gold

In this HOT Article, US researchers have presented an in depth reactivity study of alkynylgold species and phosphonates. As protodeauration is the main terminating step in gold catalysis, the effect of labile P–H bonds will be of interest to those studying gold catalysis, as well as those studying phosphite chemistry.

Read more about these gold complexes for FREE until mid-November at:

P–H activation using alkynylgold substrates: steric and electronic effects

Gerald F. Manbeck, Mark C. Kohler, Meghan R. Porter and Robert A. Stockland Jr.
Dalton Trans., 2011, Advance Article
DOI: 10.1039/C1DT11337B

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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: 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: 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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