Dalton Transactions Lecture at the University of California, Berkeley 2016

Professor Mircea Dinca

Professor Mircea Dincă (MIT, USA)

The 2015 Dalton Transactions Lecture awardee – Professor Mircea Dincă (MIT, USA) – delivered his presentation at UC Berkeley in March 2016. This Lecture is awarded annually to an exceptional young inorganic chemist in the Americas. Previous recipients are:

2014 Christine Thomas (Brandeis University)

2013 Trevor Hayton (UCSB)
2012 Teri Odom (Northwestern University)
2011 Daniel Gamelin (U Washington)
2010 Paul Chirik (Princeton University)
2009 Francois Gabbai (Texas A & M University)
2008 Dan Mindiola (Indiana University)
2007 Geoff Coates (Cornell University)
2006 John Hartwig (University of Illinois at Urbana-Champaign)
2005 Kit Cummins (MIT)

Each Dalton Transactions Lecture awardee is provided with an honorarium and a commemorative plaque.

Professor Dincă is an Assistant Professor of Chemistry at the Massachusetts Institute of Technology. His research focuses on the functional chemistry of inorganic and metal-organic materials, with a current emphasis on porous materials and high-nuclearity metal clusters.

Congratulations to Professor Dincă for his Dalton Transactions Lecture award!

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Carbon dioxide reduction put under the spotlight

Written by James Moore for Chemistry World

A team of scientists in China and France has made a rhenium-based catalyst that reduces carbon dioxide under visible light, providing a practical alternative to UV-sensitive catalysts.

By tuning the complex's ligands, researchers designed a rhenium catalyst that reduces carbon dioxide under visible light

By tuning the complex's ligands, researchers designed a rhenium catalyst that reduces carbon dioxide under visible light

With atmospheric carbon dioxide concentrations increasing, scientists are searching for ways to halt the rise. One method is to capture the gas and convert it to chemical feedstock. But significant energy is required for its conversion. Considerable effort has, therefore, been devoted to developing catalysts for carbon dioxide’s electrochemical or photochemical reduction.

Interested? The full article can be read in Chemistry World.

The original article can be read below:

Photochemical and electrochemical catalytic reduction of CO2 with NHC-containing dicarbonyl rhenium(I) bipyridine complexes
Antoine Maurin, Chi-On Ng, Lingjing Chen, Tai-Chu Lau, Marc Robert* and Chi-Chiu Ko*
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C6DT01686C

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Dalton Transactions Impact Factor – 4.177

Moving from strength to strength whilst being the largest publisher of high quality research across inorganic, organometallic and bioinorganic chemistry!

The 2015 Journal Citation Reports® have just been released and we are pleased to  announce that Dalton Transactions received an Impact Factor* of  4.177.
Graphical abstract: Front cover
We would like to thank all our authors, referees and readers who have contributed to this success, as well our Editorial and Advisory Boards for their hard work and continued support. Because of you, Dalton Transactions has continued to move from strength to strength as the largest publisher of high quality fundamental research across the fields of inorganic, organometallic and bioinorganic chemistry.

We invite you to submit your best work to Dalton Transactions!

Also of interest: Find out how other Royal Society of Chemistry journals are ranked in the latest Impact Factor release.

Take a look at a selection of our most highly cited articles listed below:

Perspectives

A golden future in medicinal inorganic chemistry: the promise of anticancer gold organometallic compounds
Benoît Bertrand and  Angela Casini
Dalton Trans., 2014, 43, 4209-4219
DOI: 10.1039/C3DT52524D

Luminescent metal–organic frameworks as explosive sensors
Debasis Banerjee, Zhichao  Hu and  Jing  Li
Dalton Trans., 2014, 43, 10668-10685
DOI: 10.1039/C4DT01196A

Communications

Pillar[5]arene-based diglycolamides for highly efficient separation of americium(III) and europium(III)
Lei Wu, Yuyu Fang, Yiming Jia, Yuanyou Yang, Jiali Liao, Ning Liu, Xinshi Yang, Wen Feng, Jialin Ming and Lihua Yuan
Dalton Trans., 2014, 43, 3835-3838
DOI: 10.1039/C3DT53336K

Full papers

Adsorption of divalent metal ions from aqueous solutions using graphene oxide
Rafal Sitko, Edyta Turek, Beata Zawisza, Ewa Malicka, Ewa Talik, Jan Heimann, Anna Gagor, Barbara Feist and Roman Wrzalik
Dalton Trans., 2013, 42, 5682-5689
DOI: 10.1039/C3DT33097D

Towards cancer cell-specific phototoxic organometallic rhenium(I) complexes
Anna Leonidova, Vanessa Pierroz, Riccardo Rubbiani, Jakob Heier, Stefano Ferrari and Gilles Gasser
Dalton Trans., 2014, 43, 4287-4294
DOI: 10.1039/C3DT51817E

*The Impact Factor provides an indication of the average number of citations per paper. Produced annually, Impact Factors are calculated by dividing the number of citations in a year, by the number of citeable articles published in the preceding two years. Data based on the 2015 Journal Citation Reports®, (Thomson Reuters, 2016).

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Dalton Transactions’ sleeping beauty and the power of tau

Dalton Transactions has been a home for high quality inorganic, organometallic and bioinorganic chemistry research since the late 1960s. One paper in particular has received resounding attention from the community and is one of the most highly cited inorganic papers of all time.

In 1984, ‘Synthesis, structure, and spectroscopic properties of copper(II) compounds containing nitrogen–sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper(II) perchlorate’ was published in the Journal of the Chemical Society, Dalton Transactions. This work was the result of a collaboration between the Addison lab at Drexel University, USA, and the Reedijk lab at Leiden University, the Netherlands. It outlines a model for the active site of the Type-1 copper protein azurin, and was the first publication to introduce the τ (tau) parameter as a structural descriptor for 5-coordinate compounds.

τ (tau) symbol
5-coordinate compound

Early citations of the work were related to copper proteins and models for them, and it was used for electron paramagnetic resonance (EPR) vs. structure correlation. However, it was not until the early 1990s that this ‘sleeping beauty’, a term coined1 for papers whose importance lies dormant for many years before they are recognized and citations start to rise, was awoken. The τ parameter, now also known as the geometry index or structural parameter, is what led to the paper’s rise in popularity. Researchers began to adopt the parameter to determine the coordination center geometry of a given molecule of interest. It has a value between 0 and 1, and when expressed in the extremes, this indicates that a molecule will either be square pyramidal or trigonal bipyramidal, respectively. The team later also developed the ‘disphenoidality’ parameter (φt) for four-coordination.

With over five and a half thousand citations to date, and a continued steady rise of approximately 10 citations a week, the significance and appreciation for this parameter is clearly shown by the community. When describing his work, Addison explains his motivation for inventing the τ -parameter “I simply couldn’t figure out how to compare differently ‘irregular’ pentacoordinate centres easily using metrics such as the Muetterties/Guggenberger2 parameter sets” and adds “I suppose this has become our “iPod” paper – the thing that people wanted, but didn’t appreciate beforehand how much they wanted it!  But a difference is that Steve Jobs actually realised in advance that people would find the iPod useful”. Addison goes on to conclude “I think it provides a demonstration of the utility of simplicity for helping in understanding otherwise complicated ideas.”

Dalton Transactions is proud to be the home of this pioneering work and eagerly awaits the break in slumber of today’s sleeping beauties.

References

1. Q. Ke, E. Ferrara, F. Radicchi, & A. Flammini,  Proc. Natl Acad. Sci., 2015, 112 (24), 7426-7431, DOI10.1073/pnas.1424329112

2. E.L. Muetterties & L.J. Guggenberger, J. Am. Chem. Soc., 1974, 96 (6), 1748-1756, DOI: 10.1021/ja00813a017

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A very warm welcome to Richard Layfield

Please join us in welcoming Professor Richard Layfield who has recently joined the Dalton Transactions Editorial Board as an Associate Editor. Based at The University of Manchester, U.K, where he is Professor of Inorganic Chemistry and Assistant Vice-Dean for Research, his research interests include lanthanide organometallic chemistry, 3d transition metal amide chemistry and carbene chemistry, applications of coordination/organometallic chemistry in molecular magnetism (particularly single-molecule magnets). He also has some interests in catalytic transformations involving heavier p-block elements.

When joining the Board, Professor Layfield said:

“I am very much looking forward to working with the Dalton Transactions team, and to contributing to developing the Editorial Board’s vision for the journal.”

Recent articles by Professor Layfield published in Dalton Transactions include:

Magnetic frustration in a hexaazatrinaphthylene-bridged trimetallic dysprosium single-molecule magnet
Richard Grindell, Veacheslav Vieru, Thomas Pugh, Liviu F. Chibotaru and Richard A. Layfield
Dalton Trans., 2016, DOI: 10.1039/C6DT01763K

Molecular and electronic structures of donor-functionalized dysprosium pentadienyl complexes
Benjamin M. Day, Nicholas F. Chilton and Richard A. Layfield
Dalton Trans., 2015,44, 7109-7113, DOI: 10.1039/C5DT00346F

Reactivity of three-coordinate iron–NHC complexes towards phenylselenol and lithium phenylselenide
Thomas Pugh and  Richard A. Layfield
Dalton Trans., 2014,43, 4251-4254, DOI: 10.1039/C3DT53203H

Sonja N. König, Nicholas F. Chilton, Cäcilia Maichle-Mössmer, Eufemio Moreno Pineda, Thomas Pugh, Reiner Anwander and Richard A. Layfield
Dalton Trans., 2014,43, 3035-3038, DOI: 10.1039/C3DT52337C
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Malcolm Green’s 80th Birthday Symposium

We are delighted to announce the success of Malcolm Green’s 80th Birthday Symposium that was held at the Inorganic Chemistry Laboratory and Balliol College, University of Oxford, UK, on 14th May 2016. Malcolm was presented with a copy of a collection of his articles published by the Royal Society of Chemistry, highlighting his vast contribution to Inorganic Chemistry over the last 50 years. Please join us in wishing Malcolm a very Happy Birthday!

Image credit: Polly Arnold

Image credits: Karl Harrison

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Malcolm Green FRS: In celebration of his 80th Birthday

Posted on behalf of F. Geoffrey N. Cloke, Philip Mountford, Dermot O’Hare, Gerard Parkin and Andrea Sella

This collection of articles is dedicated to Professor Malcolm L. H. Green on the occasion of his 80th birthday.  Malcolm was born in Eastleigh, Hampshire, on the 16th of April, 1936. He received his B. Sc. (Hons) in 1956 from the University of London (Acton Technical College) and his Ph. D. in 1959 from Imperial College of Science and Technology, where he studied under Professor Sir Geoffrey Wilkinson. Following Imperial College, Malcolm moved to Cambridge University in 1960, and finally to Oxford University in 1963, where he was appointed University Lecturer and Septcentenary Fellow in Inorganic Chemistry at Balliol College.  On the 2nd of January 1965, he married Jennifer Green (née Bilham), with whom he has also enjoyed a long time scientific collaboration.  Malcolm became a Fellow of the Royal Society in 1985 and was appointed Statutory Professor and Head of the Inorganic Chemistry Laboratory and Professorial Fellow of St. Catherine’s College in 1989.  He became a research active Emeritus Professor in 2003 and continues to publish to this day.

Professor Malcolm L. H. Green

Malcolm’s contributions to inorganic chemistry are numerous and varied.  His first publication, which bears the title “Bis‑cyclopentadienylrhenium hydride”,  appeared in 1958 and was based on his Ph. D. thesis which was entitled “A study of some transition metal hydrides and olefin complexes.”  To date, he has published more than 600 papers describing synthetic, structural, and mechanistic aspects of the chemistry of virtually every transition element.  In order to give the reader a flavour of the research that Malcolm has performed, the present collection provides a selection of his papers that have been published in journals of the Royal Society of Chemistry over a period of more than fifty years.  For example, these papers show how Malcolm’s research popularized the now ubiquitous molybdenocene and tungstenocene systems which provided evidence for alpha‑ and beta‑hydrogen migratory insertion reactions, and also early examples of C–H bond activation.

Malcolm is well known for his synthetic achievements, an important aspect of which was his development of multigram-scale metal vapour synthesis, in which metals are vapourized and condensed with a reactive ligand.  This technique allowed him to obtain molecules such as dibenzene titanium, zirconium and hafnium, the first zerovalent compounds of these elements.  Likewise, Malcolm also employed metal vapour synthesis to isolate Mo(PMe3)6, a highly reactive electron-rich molecule.

His discovery that the simple molecule (dmpe)TiCl3(CH2CH3) exhibits a direct bonding interaction between the titanium and the β‑C‑H moiety, an interaction which he named agostic, must be regarded as one of the most important discoveries in the field of organometallic chemistry.  Furthermore, in terms of mechanistic studies, Malcolm proposed a mechanism for the stereospecific Ziegler-Natta polymerization of olefins (the so-called Green-Rooney mechanism) and also, together with Mingos and Davies, formulated a series of rules to predict the stereospecificity of nucleophilic addition to p-coordinated ligands attached to a transition metal.

While Malcolm is best known for molecular chemistry, he also developed the field of organometallic solid state chemistry, which included the first example of an organometallic compound with a large second order non-linear optical behaviour, and many examples of organometallic intercalation compounds.

Malcolm’s reasearch has not been restricted to organometallic chemistry.  For example, in his later years, he focused much effort into developing the foundational chemistry of C60 and carbon nanotubes.  His research in heterogenous catalysis, in which he discovered an excellent metal carbide catalyst for the Fischer-Tropsch conversion of synthesis gas to hydrocarbons, also resulted in the creation of the Oxford Catalysts Group (subsequently Velocys), of which he is a co-founder.

Finally, it is important to note that Malcolm has contributed much to the community by his development of a new approach for classifying covalent compounds, namely the Covalent Bond Classification (CBC) method.  This approach, which offers considerable advantages over that employing oxidation states, has now been widely adopted, to the extent that it is also used in describing materials chemistry.

Not surprisingly, his research has been widely recognized by numerous awards, some of which include:  The Royal Society of Chemistry Corday‑Morgan Medal and Prize in Inorganic Chemistry (1974); the Chemistry Society Medal in Transition Metal Chemistry (1978); the Royal Society of Chemistry Tilden Lectureship and Prize (1982); The J. C. Bailar Lecture and Medal, University of Illinois (1983); the American Chemical Society Award in Inorganic Chemistry (1984); the Royal Society of Chemistry Medal in Organometallic Chemistry (1986); the Royal Society of Chemistry Sir Edward Frankland Prize (1989); The Karl‑Ziegler Prize of the Gesellschaft Deutscher Chemiker (1992); the Davy medal of the Royal Society (1995) ; American Chemical Society award in Organometallic Chemistry (1997) and The Royal Society of Chemistry Sir Geoffrey Wilkinson Medal and Prize (2000).  Other recognitions of his work include:  University of Western Ontario, Visiting Professor (1971); Ecole de Chimie and Institute des Substances Naturalles, Paris, Visiting Professor (1972); Harvard University, A. P. Sloan Visiting Professor (1973); Pacific West Coast Lecturer in Inorganic Chemistry (1977); Sherman Fairchild Visiting Scholar at the California Institute of Technology (1981); Karl Ziegler Gastprofessor, Max Plank Institute, Mulheim (1983); Hutchinson Lectureship, University of Rochester (1983); The University Lecturer in Chemistry, University of Western Ontario (1984); Debye Lecturer, Cornell University (1985); Wuhan University, PRC, Visiting Professor (1985); Julius Stieglitz Lecturer, University of Chicago (1986); Frontiers of Science Lecturer, Texas A & M University (1987); The DuPont Lecturer, Indiana University (1989/90); The Ida Beam Lecturer, University of Iowa (1990); The Glenn T. Seaborg Lecturer in Inorganic Chemistry at the University of California, Berkeley (1991); The South‑East Lecturer in Inorganic Chemistry, USA (1991); The Walter Heiber Gastprofessor, University of Munich (1991); The Pacific Coast Lecturer (1994); The Rayson Huang Visiting Lecturer, Hong Kong (1995); The A. D. Little Lecturer, Massachusetts Institute of Technology (1995); The Stauffer Lecturer, University of Southern California (1996); the Dow Lecturer at the University of Ottowa (1996); and the James Walker Memorial Lecture, University of Edinburgh (1996); Doutor Honoris Causa, University of Lisbon, Portugal (1997); The Frank Dyer Medal, University of New South Wales (1997); The Fred Basolo Medal and Lecture., Northwestern University (1998); Ernest H. Swift Lectureship, California Institute of Technology (1998); Lewis Lecture, Cambridge UK (2001); FMC Lecturer, Princeton (2001); Distinguished Visiting Professor, Hong Kong University (2002);  Eastman Company Distinguished Lecturer in Inorganic Chemistry, University of North Carolina (2002); 34th Camille and Henry Dreyfus Lecturer, Dartmouth College (2002); Raymond Siedle Lecturer, Indiana University (2004); Bert Vallee Visiting Professor at Harvard University (2004); Falk-Plaut Lecturer, Columbia University, New York (2006); Prix Franco-Briitannique, Societé,  Francaise de Chemie (2007); and, most recently, the European Prize for Organometallic Chemistry (2015).

The breadth and originality of Malcolm’s work collected here underscores his fearless and often iconoclastic approach to chemistry. Armed with his pipe and cigarette lighter (essential for checking  new products in the lab) Malcolm infected new students with his enthusiastic approach by asking them to prepare starting materials on big scales, whether it was 3 moles of trimethylphosphine, a kilogram of molybdenum pentachloride, or more than 100 grams of  tungstenocene dihydride.  Many students encountered some of his more ambitious ideas in the King’s Arms, where original experiments and apparatus were dreamed up on the back of a beer mat.  Malcolm’s seminars became legendary for the anthropomorphism of his chemical intuition, where both mechanism and apparatus were often described in mime.  Every student of Malcolm went away not only with a broad training in inorganic chemistry, from organometallic to solid state, but also with a wealth of often hilarious stories from their time in the group.

In closing, Malcolm has been at the forefront of organometallic chemistry for more than a half-century and we hope that this collection serves as a simple means to highlight some of his significant achievements.

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All-metal sandwich inspires a theoretical following

Written by Alex Pashley for Chemistry World

In the wake of the first experimentally isolated all-metal sandwich complex last year,1 two independent groups from China have put forward their theoretical take on this inorganic rarity.2,3

Researchers analysed the molecular orbitals holding the unusual all-metal sandwich complex together

Researchers analysed the molecular orbitals holding the unusual all-metal sandwich complex together

Sandwich complexes are a class of inorganic compounds, typified by ferrocene. They feature a metal ion sandwiched between two aromatic ligands, which are bound to the central metal through haptic covalent bonds. Structurally similar species to ferrocene, with different metals or coordinating ligands, are generally termed metallocenes.

Interested in reading further? The full article can be read in Chemistry World.

The original articles can be read below and are free to access until 21st June 2016

On the nature of chemical bonding in the all-metal aromatic [Sb3Au3Sb3]3− sandwich complex
Xue-Rui You, Wen-Juan Tian, Da-Zhi Li,* Ying-Jin Wang, Rui Li, Lin-Yan Feng and Hua-Jin Zhai*
Phys. Chem. Chem. Phys., 2016, 18, 13423-13431
DOI: 10.1039/C6CP00101G

Theoretical studies on the bonding and electron structures of a [Au3Sb6]3− complex and its oligomers
Wan-Lu Li, Cong-Qiao Xu, Shu-Xian Hu and Jun Li*
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C6DT00602G

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RSC Nyholm Prize for Inorganic Chemistry goes to Advisory Board member George Christou

Each year the Royal Society of Chemistry presents prizes and awards to chemical scientists who have made a considerable contribution in their area of research, in industry and academia. This year, we are delighted to announce that Dalton Transactions Advisory Board member, Professor George Christou, of the University of Florida, USA, has been awarded the 2016 RSC Nyholm Prize for Inorganic Chemistry, for his pioneering work in magnetic metal-oxo clusters and the discovery of numerous single-molecule magnets.

In celebration of the 2016 RSC Prizes and Awards, we have collected together some of the research recently published by the winners. This collection showcases articles authored by the winners from across the Royal Society of Chemistry’s journals portfolio, which are free to access for a limited period. A full list of 2016 winners and more information about RSC Prizes and Awards can be found here.

Please join us in congratulating George on this achievement!
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Nitrogen Reduction By Homogeneous Fe Complexes Revisited

Geographer Vaclav Smil described the Haber-Bosch process as the “detonator of the human population explosion” in the twentieth century, in his Nature Millennium Essay.1 Today, nearly 80% of nitrogen atoms in human tissue have been through the Haber-Bosch process;2 where nitrogen gas is converted to ammonia converted into industrial fertilizers.

The Haber-Bosch process has now entered its second century. High temperatures and pressures and a catalyst composed of magnetite (Fe3O4), wüstite (FeO) and iron(0) metal,  push the equilibrium of a mixture of pure hydrogen, nitrogen and ammonia gas towards the formation of ammonia.  Today, one of the greatest challenges of industrial chemistry is to find an alternative catalyst and process.

In 1991 Leigh et. al. reported the nitrogen of nitrogen by a homogeneous Fe complex with two chelating phosphine ligands.3 They were able to reduce N2 to ammonia (isolated as NH4+) under strongly acidic conditions. However, following this discovery, verification and mechanistic questions remained.

The previously unreported dimer

In a recent article, ‘Teaching old compounds new tricks: efficient N2 fixation by simple Fe(N2)(diphosphine)2 complexes‘ published in Dalton Transactions, , Ashley and co-workers report their investigation of the Leigh compound. They have persued a peak that was previously unaccounted for in the 31P NMR spectrum which has led them to isolate a unique dimer of this complex, bridged by molecular N2.  Comparing the reactivities of this dimer with the two monomers that feature different simple chelating phosphine ligands, they unambiguously report yields of NH3 and N2H4 after reaction with triflic acid, and discern dependences based on ligand, temperature, and solvent.

This hitherto unreported dimeric compound, and the impressive NH3/N2H4 yields achieved with the monomers tested, add a significant piece to the puzzle of how iron-mediated N2 activation occurs.

Read the full article here:

Teaching old compounds new tricks: efficient N2 fixation by simple Fe(N2)(diphosphine)2 complexes
Laurence R. Doyle, Peter J. Hill, Gregory G. Wildgoose and Andrew E. Ashley
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C6DT00884D

1V. Smil Nature 1999, 400, 415.

2R. W. Howarth Harmful Algae 2008, 8, 14.

3J. G. Leigh and M. Jimenez-Tenorio, J. Am. Chem. Soc., 1991, 113, 5862.

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