Archive for the ‘News’ Category

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

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

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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Scientists explore arsoles’ off-colour behaviour

Various 2,5-diarylarsoles showed unexpected mechanochromic properties

Various 2,5-diarylarsoles showed unexpected mechanochromic properties

Alongside inspiring puns for infantile chemistry journalists, scientists in Japan have experimentally demonstrated that a class of heteroles known as arsoles can change colour under pressure.

Theorists predicted that these arsenic-containing compounds could form interesting optical and electronic materials, based on their low aromaticity and the high barrier to structural inversion. However, the bottom line in arsole synthesis is that volatile toxic arsenic intermediates have always limited their investigation…

The full story can be read in Chemistry World.

The original article can be read below and is free to access until the 13th June 2016.:

An experimental study on arsoles: structural variation, optical and electronic properties, and emission behavior
Makoto Ishidoshiro, Hiroaki Imoto, Susumu Tanaka and Kensuke Naka*
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C6DT01010E

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Goodbye borazine, hello hydrogen

The ruthenium catalyst produces 2.7 equivalents of hydrogen from ammonia borane

The ruthenium catalyst produces 2.7 equivalents of hydrogen from ammonia borane

Scientists are a step closer to ammonia borane-powered fuel cells thanks to a ruthenium catalyst that yields an unprecedented amount of hydrogen.

In theory, each molecule of ammonia borane, H3NBH3, can release three hydrogen molecules. This high hydrogen density makes ammonia borane an ideal fuel cell material.

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

The original article can be read below and is free to access until 8th June 2016:

Dehydrogenation of ammonia borane through the third equivalent of hydrogen
Xingyue Zhang, Lisa Kam and Travis J. Williams*
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C6DT00604C

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Top 10 most accessed

The most downloaded articles from October, November and December 2015 were:

Polyvinylpyrrolidone (PVP) in nanoparticle synthesis
Kallum M. Koczkur, Stefanos Mourdikoudis, Lakshminarayana Polavarapu and Sara E. Skrabalak
Dalton Trans., 2015, 44, 17883-17905
DOI: 10.1039/c5dt02964c

Polyoxometalate – conductive polymer composites for energy conversion, energy storage and nanostructured sensors
Sven Herrmann, Chris Ritchie and Carsten Streb*
Dalton Trans., 2015, 44, 7092-7104
DOI: 10.1039/c4dt03763d

Anti-Markovnikov oxidation and hydration of terminal olefins
Jiayi Guo and Peili Teo*
Dalton Trans., 2014, 43, 6952-6964
DOI: 10.1039/c3dt53600a

Beyond iron: non-classical biological functions of bacterial siderophores
Timothy C. Johnstone and Elizabeth M. Nolan*
Dalton Trans., 2015, 44, 6320-6339
DOI: 10.1039/c4dt03559c

A cartography of the van der Waals territories
Santiago Alvarez
Dalton Trans., 2013, 42, 8617-8636
DOI: 10.1039/c3dt50599e

p-Type mesoscopic NiO as an active interfacial layer for carbon counter electrode based perovskite solar cells
Zonghao Liu, Meng Zhang, Xiaobao Xu, Lingling Bu, Wenjun Zhang, Wenhui Li, Zhixin Zhao,* Mingkui Wang,* Yi-Bing Cheng and Hongshan He*
Dalton Trans., 2015, 44, 3967-3973
DOI: 10.1039/c4dt02904f

A detailed kinetic analysis of rhodium-catalyzed alkyne hydrogenation
Jingwei Luo, Allen G. Oliver and J. Scott McIndoe*
Dalton Trans., 2013, 42, 11312-11318
DOI: 10.1039/c3dt51212f

Iridium-based complexes for water oxidation
Julianne M. Thomsen, Daria L. Huang, Robert H. Crabtree* and Gary W. Brudvig*
Dalton Trans., 2015, 44, 12452-12472
DOI: 10.1039/c5dt00863h

Morphology control of the perovskite films for efficient solar cells
Lingling Zheng, Danfei Zhang, Yingzhuang Ma, Zelin Lu, Zhijian Chen, Shufeng Wang, Lixin Xiao* and Qihuang Gong
Dalton Trans., 2015, 44, 10582-10593
DOI: 10.1039/c4dt03869j

De facto methodologies toward the synthesis and scale-up production of UiO-66-type metal–organic frameworks and membrane materials

Zhigang Hu and Dan Zhao*
Dalton Trans., 2015, 44, 19018-19040
DOI: 10.1039/c5dt03359d

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Perspectives and Frontiers by RSC award winners

We are delighted to present a selection of recently-published Dalton Transactions Perspective and Frontier articles by recent winners of Royal Society of Chemistry awards.

Adrian Chaplin

Dr Adrian Chaplin: 2015 Harrison-Meldola Memorial Prize winner

NHC-based pincer ligands: carbenes with a bite
Rhiann E. Andrew, Lucero González-Sebastián and Adrian B. Chaplin
Dalton Trans., 2016, 45, 1299
DOI:10.1039/C5DT04429D

In this frontier article we overview the emergence and scope of NHC-based CCC and CNC pincer systems, i.e. complexes containing mer-tridentate ligands bearing two NHC donor groups, comment on their effectiveness in applications, and highlight areas for future development and exploitation.

graphical abstract



Paul Dyson

Professor Paul Dyson: 2015 Bioinorganic Chemistry Award winner

Metal-based drugs that break the rules
Claire S. Allardyce and Paul J. Dyson*
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C5DT03919C

Cisplatin and other platinum compounds have had a huge impact in the treatment of cancers and are applied in the majority of anticancer chemotherapeutic regimens. The success of these compounds has biased the approaches used to discover new metal-based anticancer drugs. In this perspective we highlight compounds that are apparently incompatible with the more classical (platinum-derived) concepts employed in the development of metal-based anticancer drugs, with respect to both compound design and the approaches used to validate their utility. Possible design approaches for the future are also suggested.

graphical abstract



Dr Kogularamanan Suntharalingam

Dr Kogularamanan Suntharalingam: Dalton Young Researchers Award 2014 Winner

Advances in cobalt complexes as anticancer agents
Catherine R. Munteanu and Kogularamanan Suntharalingam*
Dalton Trans., 2015, 44, 13796-13808
DOI: 10.1039/C5DT02101D

The evolution of resistance to traditional platinum-based anticancer drugs has compelled researchers to investigate the cytostatic properties of alternative transition metal-based compounds. The anticancer potential of cobalt complexes has been extensively studied over the last three decades, and much time has been devoted to understanding their mechanisms of action. This perspective catalogues the development of antiproliferative cobalt complexes, and provides an in depth analysis of their mode of action.

graphical abstract


We will continue you update this blog post as more articles are published.

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End of year HOT articles!

December 2015’s HOT articles are here and free to access. These have also been compiled into a collection on our website.

Switching the orientation of Jahn–Teller axes in oxime-based MnIII dimers and its effect upon magnetic exchange: a combined experimental and theoretical study
Priyanka Comar, Thayalan Rajeshkumar, Gary S. Nichol, Mateusz B. Pitak, Simon J. Coles, Gopalan Rajaraman and Euan K. Brechin
Dalton Trans., 2015, 44, 19805-19811
DOI: 10.1039/C5DT03615A

graphical abstract

Free to access until 23rd December 2015


Coordination chemistry of 2,2′-biphenylenedithiophosphinate and diphenyldithiophosphinate with U, Np, and Pu
Joseph A. Macor, Jessie L. Brown, Justin N. Cross, Scott R. Daly, Andrew J. Gaunt, Gregory S. Girolami, Michael T. Janicke, Stosh A. Kozimor, Mary P. Neu, Angela C. Olson, Sean D. Reilly and Brian L. Scott
Dalton Trans., 2015, 44, 18923-18936
DOI: 10.1039/C5DT02976G

graphical abstract

Free to access until 23rd December 2015


Mechanistic features of the copper-free Sonogashira reaction from ESI-MS
Zohrab Ahmadi, Lars P. E. Yunker, Allen G. Oliver and J. Scott McIndoe
Dalton Trans., 2015, 44, 20367-20375
DOI: 10.1039/C5DT02889B

graphical abstract

Free to access until 23rd December 2015


First structural characterization of Pa(IV) in aqueous solution and quantum chemical investigations of the tetravalent actinides up to Bk(IV): the evidence of a curium break
Nidhu lal Banik, Valérie Vallet, Florent Réal, Réda Mohamed Belmecheri, Bernd Schimmelpfennig, Jörg Rothe, Rémi Marsac, Patric Lindqvist-Reis, Clemens Walther, Melissa A. Denecke and Christian M. Marquardt
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C5DT03560K

graphical abstract

Free to access until 23rd December 2015


Compositional dependence of anomalous thermal expansion in perovskite-like ABX3 formates
Ines E. Collings, Joshua A. Hill, Andrew B. Cairns, Richard I. Cooper, Amber L. Thompson, Julia E. Parker, Chiu C. Tang and Andrew L. Goodwin
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C5DT03263F

graphical abstract

Free to access until 23rd December 2015


Modular solid-phase synthesis, catalytic application and efficient recycling of supported phosphine–phosphite ligand libraries
Frank J. L. Heutz and Paul C. J. Kamer
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C5DT03226A

graphical abstract

Free to access until 23rd December 2015


Synthesis and controlled growth of osmium nanoparticles by electron irradiation
Anaïs Pitto-Barry, Luis M. A. Perdigao, Marc Walker, James Lawrence, Giovanni Costantini, Peter J. Sadler and Nicolas P. E. Barry
Dalton Trans., 2015, 44, 20308-20311
DOI: 10.1039/C5DT03205A

graphical abstract

Free to access until 23rd December 2015


Palladium(II) complexes featuring a mixed phosphine–pyridine–iminophosphorane pincer ligand: synthesis and reactivity
Thibault Cheisson and Audrey Auffrant
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C5DT02789F

graphical abstract

Free to access until 23rd December 2015


Explaining the mechanical mechanisms of zeolitic metal–organic frameworks: revealing auxeticity and anomalous elasticity
Matthew. R. Ryder and Jin-Chong Tan
Dalton Trans., 2016, Advance Article
DOI: 10.1039/C5DT03514G

graphical abstract

Free to access until 23rd December 2015


The structures of CyMe4-BTBP complexes of americium(III) and europium(III) in solvents used in solvent extraction, explaining their separation properties
Christian Ekberg, Elin Löfström-Engdahl, Emma Aneheim, Mark R. StJ. Foreman, Andreas Geist, Daniel Lundberg, Melissa Denecke and Ingmar Persson
Dalton Trans., 2015, 44, 18395-18402
DOI: 10.1039/C5DT02859K

graphical abstract

Free to access until 23rd December 2015


Stepwise assembly of mixed-metal coordination cages containing both kinetically inert and kinetically labile metal ions: introduction of metal-centred redox and photophysical activity at specific sites
Ashley B. Wragg, Alexander J. Metherell, William Cullen and Michael D. Ward
Dalton Trans., 2015, 44, 17939-17949
DOI: 10.1039/C5DT02957K

graphical abstract

Free to access until 23rd December 2015


Tin sulfide and selenide clusters soluble in organic solvents with the core structures of Sn4S6 and Sn4Se6
Mingdong Zhong, Zhi Yang, Yafei Yi, Dongxiang Zhang, Kening Sun, Herbert W. Roesky and Ying Yang
Dalton Trans., 2015, 44, 19800-19804
DOI: 10.1039/C5DT03244J

graphical abstract

Free to access until 23rd December 2015

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Adjusting the Pincer Pinch

Professor Darrin Richeson’s group has carved out an interesting organometallic niche. Their papers feature low-valent metal complexes of pincer ligands combined with detailed computational analysis of the electronic structures. In their recent Dalton Transactions article they report unique coinage metal complexes of the “PN3P” ligand below.

This "PN3P" ligand

The judicious selection of this particular pincer framework resulted in complexes with geometric properties distinct from those of the same metals with other “PNP”-type ligands. Choosing the ligand with a NR instead of a NH spacer between the pyridine and phosphine moieties enhances the donor strength of the phosphines while rendering the N atoms inert towards deprotonation.

Subtle effects of this adjustment manifest themselves in dramatic changes in the solid-state coordination and geometric properties of their Cu and Ag complexes. Their reported CuBr complex is coordinated by one PN3P ligand and has a distorted trigonal pyramidal geometry. They contrast these to Cu(I) complexes of an analogous PN3P ligand with NH spacers, which coordinate two ligands and in one case displace the halide atom. Using CH2 spacers, a previously reported Cu(I) structure exhibits T-shaped geometry and a non-coordinating triflate anion. The Cu(I) reported here shows a geometry much closer to trigonal pyramidal, with a coordinating triflate anion.

The second part of the paper discusses details of the electronic structure gleaned from DFT calculations. Particularly illuminating is a paragraph on page 19157, summarizing the particulars of the bonding as “a balance of bonding and antibonding interactions…diffuse polarized-π orbitals…(and) back donation.” Perhaps this seems summary seems unsurprising, but there are subtleties in the analysis.

Professor Richeson was my M.Sc. supervisor (I finished in his group six years ago). I write this in gratitude for his mentorship, and in appreciation of his group’s continuing work.

For more details read the full paper:

Coinage metal complexes supported by a “PN3P” scaffold
Gyandshwar Kumar Rao, Serge I. Gorelsky, Ilia Korobkov and Darrin Richeson
Dalton Trans., 2015,44, 19153-19162
DOI: 10.1039/C5DT03515E


Ian Mallov Ian Mallov is currently a Ph.D. student in Professor Doug Stephan’s group at the University of Toronto. His research is focused on synthesizing new Lewis-acidic compounds active in Frustrated Lewis Pair chemistry. He grew up in Truro, Nova Scotia and graduated from Dalhousie University and the University of Ottawa, and worked in chemical analysis in industry for three years before returning to grad school.
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