Dalton Transactions Blog

To me the most interesting observation in the recent Dalton Transactions paper from the group of Professor Phil Power was their suggestion that secondary interactions between dicoordinate Fe(II) atoms and carbon atoms on their ligands probably have a significant effect on the magnetic moment of the complexes.

Specifically, they postulate that these interactions help to quench the orbital contribution to the magnetic moment, which is significant for other dicoordinate Fe(II) complexes studied.

But let’s take a step back.  Dicoordinate Iron(II) complexes were unknown until the 1980’s, thought to be too unstable to isolate and structurally characterize.  As the authors detail, examples were discovered gradually. All featuring large coordinating ligands bound through anionic C, N, or O donors.  Power reports a total of thirty currently known.

No one, it appears, has previously undertaken thorough magnetic studies.  Indeed, do you remember studying how crystal field theory applies to dicoordinate metal species in your introductory inorganic class?  I don’t.

The authors focus their attention on four species. Two of these feature large silylamido ligands and have solid-state N-Fe-N angles of 169^o and 172^o, the other have two large aryl ligands and exhibit slightly more bent geometries.  The authors support the evidence that a significant part of the measured temperature-dependent magnetic moment of these molecules arises from the orbital contribution – that is, from the motion of electrons around the iron nucleus, rather than arising only from the spin contribution, the electrons spinning about their own axes.

However, the less linear aryl iron(ll) complexes show the greater orbital contribution to the magnetic moment, which brings me back to the beginning.  This is a thorough paper; the authors also construct a spectrochemical series for the dicoordinate Fe(II) complexes and exactingly compare computed and experimental magnetic data.  But the original small structure-function observation fascinated me on my first reading.

Read the full article now:

Ligand field influence on the electronic and magnetic properties of quasi-linear two-coordinate iron(II) complexes
Nicholas F. Chilton, Hao Lei, Aimee M. Bryan, Fernande Grandjean, Gary J. Long and Philip P. Power
Dalton Trans., 2015, 44, 11202-11211
DOI: 10.1039/C5DT01589H

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.

The 2014 Dalton Transactions Lecture awardee – Professor Christine Thomas (Brandeis University) – delivered her presentation at UC Berkeley last month. This Lecture is awarded annually to an exceptional young inorganic chemist in the Americas. Previous recipients are:

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 Thomas is an Associate Professor of Chemistry at Brandeis University, and her research program focuses on synthetic inorganic, organometallic and bioinorganic chemistry.

In 2010, Professor Thomas was selected for the U.S. Department of Energy’s Early Career Research Program and in 2011, she was named a Alfred P. Sloan Fellow. Christine is also the recipient of a 2012 National Science Foundation CAREER award and was selected as a 2012 Organometallics Fellow and a 2013/2014 Chemical Communications Emerging Investigator. Her dedication to teaching was recognized with The 2012 Michael L. Walzer ’56 Award for Excellence in Teaching at Brandeis. In 2012, she joined the Advisory Board for Chemical Communications and, as of May 2014, she is an Associate Editor for Dalton Transactions.

Congratulations to Professor Thomas for her Dalton Transactions Lecture award!

We are pleased to congratulate Henryk Kozłowski, a Chartered Scientist of the Royal Society of Chemistry, on his 70^th birthday and >90 articles in Dalton Transactions (including Journal of the Chemical Society, Dalton Transactions).

Dalton Transactions is delighted to be sponsoring the XIII International Symposium on Inorganic Biochemistry, organized between 1st and 6th September 2015 in Karpacz, Poland. The first International Symposium on Inorganic Biochemistry, first of the series of conferences organized by Henryk, also took place in Karpacz, and now, three decades later, it is there again, in close proximity to where it took place for the first time. This year’s conference will be quite special; we will all celebrate Henryk’s very important anniversary.

As usual, the conference aims to provide a valuable discussion forum on recent advances in cross-cutting fields of inorganic, coordination and bioinorganic chemistry with biology and medicine, in particular discussing topics such as chemical structure and thermodynamics, solution equilibria and coordination chemistry of metals with biomolecules; transport, homeostasis and toxicity of metals in diseases; metal-based therapy and diagnostics. More information will soon be available at www.henryk.uni.wroc.pl.

Henryk Kozłowski is the founder of Polish bioinorganic chemistry, currently working at the interface between chemistry and biology. At the Department of Chemistry, University of Wroclaw, he created one of the most dynamic research teams – the Bioinorganic and Biomedical Chemistry group. Apart from his contribution to the Royal Society of Chemistry, the list of his most important honors and awards include: the Membership of the Polish Academy of Sciences and the National Science Centre, honorary doctorates from the Taras Shevchenko University in Kiev and the University of Gdansk, the prestigious Marie Curie National Science Award in Chemistry and numerous awards of the Minister of Polish Science.

Henryk has been a visiting Professor at the Universities of Strasbourg, Siena, Ferrara, Florence, Sassari, Cagliari, Lille, Dunkirk and Paris. His scientific achievements include 33 supervised PhDs, a Hirsch index of 42, over 500 original papers, 17 book chapters, over 350 invited lectures given at international conferences and at various universities; he has been cited over 9400 times.

Happy birthday, Henryk!

Professor Robert (Bob) Williams died this March at the age of 89. He was a true pioneer in the field of bio-inorganic chemistry – especially concerning the role of calcium as a biological messenger – and contributed substantially to our understanding of the evolution of life. Professor Williams was often considered as one of the first people to start thinking about metallomics as a field, and will be greatly missed amongst his peers.

In memory of Professor Williams’ huge contribution to the field, we have collated a number of his publications across Metallomics, Dalton Transactions and ChemComm below. We hope you enjoy revisiting some of his exceptional work.

Copper proteomes, phylogenetics and evolution, L. Decaria, I. Bertini, R.J.P. Williams, Metallomics, 2011, 56–60

Zinc proteomes, phylogenetics and evolution, L. Decaria, I. Bertini, R.J.P. Williams, Metallomics, 2010, 706–709

A chemical systems approach to evolution, R.J.P. Williams, Dalton Transactions, 2007, 991–1001

Metallo-enzyme catalysis, R.J.P. Williams, Chemical Communications, 2003, 1109–1113

The chemical elements of life, R.J.P. Williams, Journal of the Chemical Society, Dalton Transactions, 1991, 539–546

Temperature study of the solution conformations of aqueous lanthanide(III) complexes containing monodentate ligands, A.L. Du Preez, S. Naidoo, R.J.P. Williams, Journal of the Chemical Society, Dalton Transactions, 1988, 2315–2321

A proton NMR study of some CoII complexes containing the N-hexadecyl-iminodiacetate ligand, C.J. Rix, R.J.P. Williams, Journal of the Chemical Society, Chemical Communications, 1986, 203–205

Solution conformation of aqueous lanthanide(III)-antipyrine complexes, A.L. Du Preez, R.J.P. Williams, Journal of the Chemical Society, Dalton Transactions, 1986, 1425–1429

Precipitation within unilamellar vesicles. Part 1. Studies of silver(I) oxide formation, S. Mann, R.J.P. Williams, Journal of the Chemical Society, Dalton Transactions, 1983, 311–316

Precipitation within unilamellar vesicles. Part 2. Membrane control of ion transport, S. Mann, M.J. Kime, R.G. Ratcliffe, R.J.P. Williams, Journal of the Chemical Society, Dalton Transactions, 1983, 771–774

The characterisation of the nature of silica in biological systems, S. Mann, C.C. Perry, R.J.P. Williams, C.A. Fyfe, G.C. Gobbi, G.J. Kennedy, Journal of the Chemical Society, Chemical Communications, 1983, 168–170

New organo-metallic reagents for electron microscopy, S. Mann, R.J.P. Williams, P.R. Sethuraman, M.T. Pope, Journal of the Chemical Society, Chemical Communications, 1981, 1083–1084

Solid state phosphorus NMR spectroscopy of minerals and soils, R.J.P. Williams, R.G.F. Giles, A.M. Posner, Journal of the Chemical Society, Chemical Communications, 1981, 1051–1052

Electron relaxation rates of lanthanide aquo-cations, B.M. Alsaadi, F.J.C. Rossotti, R.J.P. Williams, Journal of the Chemical Society, Dalton Transactions, 1980, 2147–2150

Hydration of complexone complexes of lanthanide cations, B.M. Alsaadi, F.J.C. Rossotti, R.J.P. Williams, Journal of the Chemical Society, Dalton Transactions, 1980, 2151–2154

Preparation of Ag2O crystallites within phospholipid vesicles and their use in nucleation studies, J.L. Hutchison, S. Mann, A.J. Skarnulis, R.J.P. Williams, Journal of the Chemical Society, Chemical Communications, 1980, 634–635

Studies of lanthanide (III) dipicolinate complexes in aqueous solution. Part 2. Hydration, B.M. Alsaadi, F.J.C. Rossotti, R.J.P. Williams, Journal of the Chemical Society, Dalton Transactions, 1980, 813–816

Studies of lanthanide(III) pyridine-2,6-dicarboxylate complexes in aqueous solution. Part 1. Structures and 1H nuclear magnetic resonance spectra, B.M. Alsaadi, F.J.C. Rossotti, R.J.P. Williams, Journal of the Chemical Society, Dalton Transactions, 1980, 597–602

Location of biological compartments by high resolution NMR spectroscopy and electron microscopy using magnetite-containing vesicles, S. Mann, A.J. Skarnulis, R.J.P. Williams, Journal of the Chemical Society, Chemical Communications, 1979, 1067–1068

Mapping organic molecules in biological space by high resolution NMR spectroscopy and electron microscopy, A.J. Skarnulis, P.J. Strong, R.J.P. Williams, Journal of the Chemical Society, Chemical Communications, 1978, 1030–1032

An investigation of some potential uses of the gadolinium(III) ion as a structural probe, E.C.N.F. Geraldes, R.J.P. Williams, Journal of the Chemical Society, Dalton Transactions, 1977, 1721–1726

Structure of lanthanide(III) mono- and bis-dipicolinates in solution, B.M. Alsaadi, F.J.C. Rossotti, R.J.P. Williams, Journal of the Chemical Society, Chemical Communications, 1977, 527–529

Assignment of the NMR spectrum of iron(III) protoporphyrin IX dicyanide using paramagnetic shift and broadening probes, J.G. Brassington, R.J.P. Williams, P.E. Wright, Journal of the Chemical Society, Chemical Communications, 1975, 338–340

Conformational studies of peroxidase-substrate complexes. Structure of the indolepropionic acid-horseradish peroxidase complex, P.S. Burns, R.J.P. Williams, P.E. Wright, Journal of the Chemical Society, Chemical Communications, 1975, 795–796

The temperature dependence of some physical properties of cobinamides and cobalamins, S.A. Cockle, O.D. Hensens, H.A.O. Hill, R.J.P. Williams, Journal of the Chemical Society, Dalton Transactions, 1975, 2633–2634

Conformational studies of lanthanide complexes with carboxylate ligands, B.A. Levine, J.M. Thornton, R.J.P. Williams, Journal of the Chemical Society, Chemical Communications, 1974, 669–670

Ethylenediaminetetra-acetato-lanthanate(III), -praesodimate(III), -europate(III), and -gadolinate(III) complexes as nuclear magnetic resonance probes of the molecular conformations of adenosine 5′- monophosphate and cytidine 5′-monophosphate in solution, C.M. Dobson, R.J.P. Williams, A.V. Xavier, Journal of the Chemical Society, Dalton Transactions, 1974, 1762–1764

Intramolecular nuclear Overhauser effects in proton magnetic resonance spectra of proteins, I.D. Campbell, C.M. Dobson, R.J.P. Williams, Journal of the Chemical Society, Chemical Communications, 1974, 888–889

Lanthanoid(III) cations as nuclear magnetic resonance conformational probes: Studies on cytidine 5′-monophosphate at pH 2, C.D. Barry, C.M. Dobson, R.J.P. Williams, A.V. Xavier, Journal of the Chemical Society, Dalton Transactions, 1974, 1765-1769

Nuclear magnetic resonance spectra of dimeric cupric compounds, W. Byers, R.J.P. Williams, Journal of the Chemical Society, Dalton Transactions, 1973, 555–560

Separation of contact and pseudo-contact contributions to shifts induced by lanthanide(III) ions in nuclear magnetic resonance spectra, C.M. Dobson, R.J.P. Williams, A.V. Xavier, Journal of the Chemical Society, Dalton Transactions, 1973, 2662–2664

The effect of 1,3,5-trinitrobenzene on 1H nuclear magnetic resonance and electron paramagnetic resonance spectra of some cobalt(II) porphyrins, H.A.O. Hill, P.J. Sadler, R.J.P. Williams, Journal of the Chemical Society, Dalton Transactions, 1973, 1663–1667

Origin of lanthanide nuclear magnetic resonance shifts and their uses, B. Bleaney, C.M. Dobson, B.A. Levine, R.B. Martin, R.J.P. Williams, A.V. Xavier, Journal of the Chemical Society, Chemical Communications, 1972, 791b–793

The chemistry of vitamin B12. Part XVI. Binding of thiols to the cobalt(II) corrins, S. Cockle, H.A.O. Hill, S. Ridsdale, R.J.P. Williams, Journal of the Chemical Society, Dalton Transactions, 1972, 297–302

A method of assigning 13C nuclear magnetic resonance spectra using europium(III) ion-induced pseudocontact shifts and C-H heteronuclear spin decoupling techniques, B. Birdsall, J. Feeney, J.A. Glasel, R.J.P. Williams, A.V. Xavier, Journal of the Chemical Society D: Chemical Communications, 1971, 1473–1474

Methylation by methyl vitamin B12, G. Agnes, S. Bendle, H.A.O. Hill, F.R. Williams, R.J.P. Williams, Journal of the Chemical Society D: Chemical Communications, 1971, 850–851

Kinetics of substitution of co-ordinated carbanions in cobalt(III) corrinoids, H.A.O. Hill, J.M. Pratt, S. Ridsdale, F.R. Williams, R.J.P. Williams, Journal of the Chemical Society D: Chemical Communications, 1970, 341

Thallium(I) as a potassium probe in biological systems, J.P. Manners, K.G. Morallee, R.J.P. Williams, Journal of the Chemical Society D: Chemical Communications, 1970, 965–966

The lanthanide cations as nuclear magnetic resonance probes of biological systems, K.G. Morallee, E. Nieboer, F.J.C. Rossotti, R.J.P. Williams, A.V. Xavier, R.A. Dwek, Journal of the Chemical Society D: Chemical Communications, 1970, 1132–1133