Biography

Click here for current PhD opportunities in CHE. But feel free to email me to discuss projects outside these areas and alternative sources of funding.

Manfred Bochmann is Professor of Inorganic Chemistry. He gained his Diploma Degree at Marburg University, Germany (1977), and his Ph.D. at Imperial College London, with Professor Sir Geoffrey Wilkinson (1979). After a spell in industry at ICI's Corporate Laboratory, he moved to a lectureship at UEA and became Professor of Chemistry in 1994. From 1995 -2000 he was Head of the Inorganic and Structural at the University of Leeds. He returned to UEA in April 2000. From 2006 – 2009 he was Head of the School of Chemical Sciences and Pharmacy and 2009-2011 Head of the School of Chemistry. In 2003 he was awarded the Royal Society of Chemistry Medal for Organometallic Chemistry.  

He was a vice-president of the RSC Dalton Division Council, an editorial board member of Dalton Transactions and the Journal of Organometallic Chemistry and a volume editor of a major reference work, “Comprehensive Organometallic Chemistry III” and Associate Editor of Organometallics 2006 - 2015. He is the author of two popular “Chemistry Primer” teaching texts in Organometallic Chemistry, co-author of the textbook Cotton, Wilkinson, Murillo and Bochmann: “Advanced Inorganic Chemistry”, 6th ed. (Wiley 1999), and author of the textbook "Organometallics and Catalysis: An Introduction" (OUP, 2014). 

He was a Leverhulme Trust Research Fellow (2011-12) and is an ERC Advanced Grant holder (2014-2019).

Professor Bochmann’s research centres broadly around synthetic organometallic and coordination chemistry directed towards homogeneous catalysis. He has published over 280 papers and patents in this area. He was coordinator of the EC Research Training Network on new polyolefin materials and is currently a partner in an EU-funded consortium including DSM, Sabic and Lanxess, on “Methylaluminoxane Activators in the Molecular Polyolefin Factory” (MAO-Robots). He currently heads an ERC project on synthetic gold chemistry, exploring the chemistry of gold hydrides, CO complexes, as well as their photoluminescence and anti-cancer properties. His work is supported by the ERC, EPSRC, Royal Society, British Council, European Commission, BP Chemicals, Bayer AG, and Lanxess Inc., Canada and SABIC Global Technologies.

You can follow us on twitter: https://twitter.com/BochmannGroup

ORCID ID 0000-0001-7736-5428 

Selected Publications

D. Di, A. S. Romanov, L. Yang, J. M. Richter, J. P. H. Rivett, S. Jones, T. H. Thomas, M. A. Jalebi, R. H. Friend, M. Linnolahti, M. Bochmann, D. Credgington: High-performance light-emitting diodes based on carbene-metal-amides. Science 2017, 356, 159–163.
DOI: 10.1126/science.aah4345

L. Currie, J. Fernandez-Cestau, L. Rocchigiani, B. Bertrand, S. J. Lancaster, D. L. Hughes, H. Duckworth, S. Jones, Dan Credgington, T. J. Penfold, M. Bochmann: Luminescent Gold(III) thiolates: Supramolecular interactions trigger and control switchable photoemissions from bimolecular excited statesChem Eur. J. 2017, 23, 105-113.
DOI: 10.1002/chem.201603841. "Hot" paper. 

A. Pintus, L. Rocchigiani, J. Fernandez-Cestau, P. H. M. Budzelaar, M. Bochmann: Stereo- and Regioselective Alkyne Hydrometallation with Gold(III) HydridesAngew. Chem. Int. Ed. 2016, 55, 12321–12324.
DOI: 10.1002/anie.201607522. VIP paper. 

Perspective Article:
D.-A. Roşca, J. A. Wright and M. Bochmann:
An element through the looking glass: Exploring the Au-C, Au-H and Au-O energy landscape
Dalton Transactions 2015, 44, 20785 – 20807
DOI: http://dx.doi.org/10.1039/C5DT03930D

D.-A. Roşca, J. Fernandez-Cestau, J. Morris, J. A. Wright, M. Bochmann
Gold(III) CO and CO2 Complexes and Their Role in the Water-Gas Shift Reaction
Sci. Adv. 2015, 1, e1500761.
DOI: 10.1126/sciadv.1500761

D.-A.  Roşca, J. A. Wright, D. L. Hughes, M. Bochmann.
Gold peroxide complexes and the conversion of hydroperoxides into gold hydrides by successive oxygen-transfer reactions.
Nat. Commun. 2013, 4, 2167.
DOI: 10.1038/ncomms3167

F. Ghiotto, C. Pateraki, J. R. Severn, N. Friederichs, M. Bochmann.
Rapid Evaluation of Catalysts and MAO Activators by Kinetics: What controls polymer molecular weight and activity in metallocene / MAO catalysts?
Dalton Trans. 2013, 42, 9040-9048.
DOI: 10.1039/C3DT00107E

D.-A. Roşca, D. A. Smith, D. L. Hughes, M. Bochmann.
A Thermally Stable Gold(III) Hydride: Synthesis, Reactivity, and Reductive Condensation as a new Route to AuII Complexes.
Angew. Chem. 2012, 124, 10795–10798;
Angew. Chem. Int. Ed. 2012, 51, 10643 –10646. VIP paper.
DOI: 10.1002/anie.201206468
 
M. Bochmann.
The Chemistry of Catalyst Activation: The Case of Group 4 Polymerization Catalysts.
Organometallics 2010, 29, 4711 – 4740.
DOI: 10.1021/ar100044s

All Publications

<- Page 1 of 8 ->

Rocchigiani, L., Fernandez-Cestau, J., Agonigi, G., Chambrier, I., Budzelaar, P., Bochmann, M.

(2017)

Gold(III) Alkyne Complexes: Bonding and Reaction Pathways,

in Angewandte Chemie International Edition

56

(44)

pp. 13861–13865

Full Text UEA Repository

(Article)

(E-pub ahead of print)


Romanov, A. S., Bochmann, M.

(2017)

Synthesis, structures and photoluminescence properties of silver complexes of cyclic (alkyl)(amino)carbenes,

in Journal of Organometallic Chemistry

847

pp. 114-120

Full Text UEA Repository

(Article)

(Published)


Williams, M., Green, A. I., Fernandez-Cestau, J., Hughes, D. L., O'Connell, M. A., Searcey, M., Bertrand, B., Bochmann, M.

(2017)

(C^Npz^C)AuIII complexes of acyclic carbene ligands: synthesis and anticancer properties,

in Dalton Transactions

46

(39)

pp. 13397–13408

Full Text UEA Repository

(Article)

(Published)


Fernandez Cestau, J., Bertrand, B., Pintus, A., Bochmann, M.

(2017)

Synthesis, Structures and Properties of Luminescent (C^N^C)gold(III) Alkyl Complexes: Correlation between Photoemission Energies and C-H Acidity,

in Organometallics

36

(17)

pp. 3304-3312

Full Text UEA Repository

(Article)

(Published)


Bertrand, B., Fernandez-Cestau, J., Angulo, J., Cominetti, M. M., Waller, Z. A., Searcey, M., O'Connell, M. A., Bochmann, M.

(2017)

Cytotoxicity of Pyrazine-Based Cyclometalated (C^Npz^C)Au(III) Carbene Complexes: Impact of the Nature of the Ancillary Ligand on the Biological Properties,

in Inorganic Chemistry

56

(10)

pp. 5728–5740

Full Text UEA Repository

(Article)

(Published)


Rocchigiani, L., Fernandez Cestau, J., Budzelaar, P., Bochmann, M.

(2017)

Arene C-H activation by gold(III): Solvent-enabled proton shuttling, and observation of a pre-metallation Au-arene intermediate,

in Chemical Communications

53

(31)

pp. 4358-4361

Full Text UEA Repository

(Article)

(Published)


Di, D., Romanov, A. S., Yang, L., Richter, J. M., Rivett, J. P. H., Jones, S., Thomas, T. H., Jalebi, M. A., Friend, R. H., Linnolahti, M., Bochmann, M., Credgington, D.

(2017)

High-performance light-emitting diodes based on carbene-metal-amides,

in Science

356

(6334)

pp. 159-163

Full Text UEA Repository

(Article)

(Published)


Chambrier, I., Roşca, D., Fernandez-Cestau, J., Hughes, D. L., Budzelaar, P. H. M., Bochmann, M.

(2017)

Formation of Gold(III) Alkyls from Gold Alkoxide complexes,

in Organometallics

36

(7)

pp. 1358–1364

Full Text UEA Repository

(Article)

(Published)


Romanov, A. S., Becker, C. R., James, C. E., Di, D., Credgington, D., Linnolahtu, M., Bochmann, M.

(2017)

Copper and Gold Cyclic (Alkyl)(amino)carbene Complexes with Sub-Microsecond Photoemissions: Structure and Substituent Effects on Redox and Luminescent Properties,

in Chemistry - A European Journal

23

(19)

pp. 4625–4637

Full Text UEA Repository

(Article)

(Published)


Bochmann, M., Romanov, A., Credgington, D., Di, D., Yang, L.

(2017)

Metal Complexes,

(Other contribution)

(Published)


Currie, L., Fernandez-Cestau, J., Rocchigiani, L., Bertrand, B., Lancaster, S. J., Hughes, D. L., Duckworth, H., Jones, S. T. E., Credgington, D., Penfold, T. J., Bochmann, M.

(2017)

Luminescent gold(III) thiolates: Supramolecular interactions trigger and control switchable photoemissions from bimolecular excited states,

in Chemistry - A European Journal

23

(1)

pp. 105–113

Full Text UEA Repository

(Article)

(Published)


Pintus, A., Rocchigiani, L., Fernandez-Cestau, J., Budzelaar, P. H., Bochmann, M.

(2016)

Stereo- and Regioselective Alkyne Hydrometallation with Gold(III) Hydrides,

in Angewandte Chemie International Edition

55

(40)

pp. 12321–12324

Full Text UEA Repository

(Article)

(Published)


Romanov, A. S., Di, D., Yang, L., Fernandez-Cestau, J., Becker, C. R., James, C. E., Zhu, B., Linnolahti, M., Credgington, D., Bochmann, M.

(2016)

Highly photoluminescent copper carbene complexes based on prompt rather than delayed fluorescence,

in Chemical Communications

52

(38)

pp. 6379-6382

Full Text UEA Repository

(Article)

(Published)


Rosca, D., Bochmann, M.

(2016)

Photochemical Disproportionation of an Au(II) Pincer Complex: Synthesis and Structure of an Au(I)4Au(III)4 Macrocycle,

in Organometallics

35

(1)

pp. 27-31

Full Text UEA Repository

(Article)

(Published)


Rosca, D., Wright, J., Bochmann, M.

(2015)

An element through the looking glass: Exploring the Au-C, Au-H and Au-O energy landscape,

in Dalton Transactions

44

pp. 20785-20807

Full Text UEA Repository

(Article)

(Published)


Rosca, D., Fernandez Cestau, J., Morris, J., Wright, J., Bochmann, M.

(2015)

Gold(III)-CO and gold(III)-CO2 complexes and their role in the water-gas shift reaction,

in Science Advances

1

(9)

article no. e1500761

Full Text UEA Repository

(Article)

(Published)


Roşca, D., Fernandez-Cestau, J., Romanov, A. S., Bochmann, M.

(2015)

Synthesis, C–N cleavage and photoluminescence of gold(III) isocyanide complexes,

in Journal of Organometallic Chemistry

792

pp. 117–122

Full Text UEA Repository

(Article)

(Published)


Chambrier, I., Banerjee, C., Remiro-Buenamañana, S., Chao, Y., Cammidge, A. N., Bochmann, M.

(2015)

Synthesis of Porphyrin–CdSe Quantum Dot Assemblies: Controlling Ligand Binding by Substituent Effects,

in Inorganic Chemistry

54

(15)

pp. 7368–7380

Full Text UEA Repository

(Article)

(Published)


Kuklin, M. S., Hirvi, J. T., Bochmann, M., Linnolahti, M.

(2015)

Towards Controlling the Metallocene/Methylaluminoxane Catalyzed Olefin Polymerization Process by a Computational Approach,

in Organometallics

34

(14)

pp. 3586-3597

Full Text UEA Repository

(Article)

(Published)


Remiro Buenamanana, S., Diaz-Moscoso, A., Hughes, D., Bochmann, M., Tizzard, G. J., Coles, S. J., Cammidge, A.

(2015)

Synthesis of Meso-Substituted Subphthalocyanine-Subporphyrin Hybrids: Boron SubTriBenzoDiAzaPorphyrins (SubTBDAPs),

in Angewandte Chemie-International Edition

54

(26)

pp. 7510-7514

Full Text UEA Repository

(Article)

(Published)


<- Page 1 of 8 ->

Key Research Interests

Group news 

December 2016

The Bochmann Group Christmas outing!

 

 

June 2016

Organometallics book by Manfred

Oxford University Press and Chemical Industry Press, Beijing, have signed an agreement to translate Organometallics and Catalysis into Chinese and to distribute the book in Mainland China. This follows an agreement in May 2015 to translate into Korean. This textbook is aimed at providing an introduction into organometallic and catalytic methods for advanced undergraduates and postgraduates.  

Chemistry Means Business: “One-to-Watch” Prize to Dr Romanov

Dr Romanov and some light-emitting diodes

Alex Romanov, together with Dawei Di representing our collaborators at the Optoelectronic Lab, Cambridge University, has presented our work on new types of photo-emitting materials for organic light-emitting diodes at the international RSC Chemistry Means Business competition in London. He was awarded the “One-to-Watch” Prize and has been invited to attend a business mentoring course at the Judge Business School, Cambridge.

The work concerns new materials for highly efficient light emitting diodes with up to 100% internal quantum efficiency and 27% external quantum efficiency, a record for a solution-processed OLED device. The work arose as the unexpected outcome of fundamental studies in gold chemistry and is based on a new light emission mechanism enabled by intramolecular rotation. The OLEDs show very high brightness, with low turn-on voltage. The results have so far been the subject of two patent applications by UEA, plus another one headed by Cambridge.

April 2016

UEA research at the Chemistry Means Business event

Alex Romanov’s project on “High-performance coinage metal emitters for the solution-processed OLED technology” has been selected as one of the finalists of the Royal Society of Chemistry’s Chemistry Means Business event, due to take place 15-16 June in London. 

The selection means that Alex will give a presentation to potential investors in this year’s Emerging Technologies Competition final. 

Many congratulations Alex!

This project arose from a chance observation that gold complexes of certain types of carbene ligands show photoluminescence. This led to the establishment of a collaboration with the Optoelectronics Group at the Cavendish Laboratory, Cambridge, in March 2015. The joint work has so far produced the most energy-efficient solution-processed organic light emitting diode (OLED) reported to-date. Solution processing is set to replace thermal vapour deposition technology which is the current state-of-the-art. 

7th March

Alex Romanov is presenting his results to MPs in London: SET Britain competition at the Houses of Parliament. Here shown with Norwich MP Clive Lewis.

Alex synthesized new photoluminescent copper and gold carbene complexes which proved to give organic light emitting diodes (OLEDs) with record external quantum efficiency. The work was done in collaboration with the Physics Department at Cambridge University.

 

Alex Romanov with Norwich MP Clive Lewis

January

The Dalton Transactions Perspective article "An element through the looking glass: exploring the Au–C, Au–H and Au–O energy landscape" made the cover page:  See a PDF of the cover here and read the publication here.

Dalton Transactions cover photo

2015

December
Christmas time for the Bochmann group!

The Bochmann Group Christmas meal

The Bochmann Group Christmas meal

The Bochmann Group Christmas meal

16 October:
Congratulations to Julio, James and former co-worker Dragos on the publication of their Science Advances paper "Gold(III) CO and CO2 Complexes and Their Role in the Water-Gas Shift Reaction" reporting the first example of an isolable CO complex of Au(III) and the first CO2 complex of gold, as well as why their reactivity differs so drastically from that of platinum. Thanks for all the hard work!

See the publication at http://advances.sciencemag.org/content/1/9/e1500761.

16 September 2015
Alex Romanov wins First Prize for the best talk at the Chemistry Research Day, for his presentation on new copper and gold carbene complexes as bright photoemitters in light-emitting diodes. 

Alex Romanov

Benoit Bertrand wins prize for his poster presentation on gold complexes and their biological activity at the School Research Day.

Benoit Bertrand

 

March 2015

Anna Pintus image

Dr. Anna Pintus joins the group from the University of Cagliari, Sardinia. Anna has a degree in biology, which, rather unusually, she followed by a PhD in inorganic chemistry on the topic of gold and platinum dithiolene complexes for photovoltaic applications. This has provided her with experience in synthesis as well as electrochemistry, fluorescence spectroscopy and computational techniques. She also spent about 6 months at Stanford University as a Fulbright Fellow, followed by a Postdoc position with Prof. V. Lippolis at Cagliari.

16 February 2015

Dr Benoit Bertrand image

Dr Benoit Bertrand joins the group. Benoit completed an interdisciplinary PhD degree from the University of Burgundy at Dijon, where he carried out the synthesis of gold complexes under the supervision of Prof. P. Le Gendre, and the University of Groningen Pharmacy department, where he conducted cytotoxicity and biological studies on the effect of his gold compounds and acquired skills in biological methods and cell culture handling under the supervision of Profs. G. Groothuis and A. Casini.

28 January 2015: Chrisa Pateraki successfully defended her PhD thesis

Image of Chrisa Pateraki

Chrisa has carried out her PhD studies as part of an EU Research Consortium entitled “MAO Robots”, funded by the European Commission. Her work was concerned with identifying the formation, structure and activator effects of methylaluminoxane (MAO), an important activator for metallocene-type olefin polymerisation catalysts that is widely used in industry. Chrisa’s work centred on the identification of the first steps of the reaction of trimethylaluminium with water, the modification of MAO, and the establishment of structure-activity relationships of different MAO grades by in-situ polymerisation kinetics methods. Many congratulations Chrisa!

December 2014: The new book has appeared:

Organometallics book by Manfred

After much blood, sweat and (almost) tears: Organometallics and Catalysis, an Introduction. 410 pages. Oxford University Press, £32.99. A textbook aimed at undergraduates and postgraduate students with a research focus on organometallic chemistry. The book covers main group organometallics, transition metals and the main catalytic systems. Enjoy!

October 2014

Morwen Williams image

After graduating with a First Class degree in Biological and Medicinal Chemistry from the University of Exeter. Morwen (Moz) will work on a project designing gold complexes for selective cytotoxicity. The project is co-supervised by Professor Mark Searcey of the School of Pharmacy.

Lucy Curry image

Lucy Curry joins the group as a new PhD student
Lucy graduated from Oxford University where she carried out a Part II project on late transition metals chemistry with Prof. Andrew Weller. Lucy will explore new bonding types in gold chemistry including gold clusters and their photoluminescence.

23 July 2014:

The traditional Group outing to the Norfolk Broads.

7-11 July 2014:  Dragos presenting posters at the Organometallics Gordon Conference, Salve Regina University, Newport, Rhode Island.

Drago Rosca and his poster

25 May 2014: Maria Blaya from the University of Murcia, Spain, is joining the group as a visiting PhD student, as part of the requirements of a European PhD sponsored by the Spanish Government. Maria will be working on cyclometallation reactions of gold, in conjunction with Julio.

Maria Blaya photo

28 March 2014: Dragos passed his PhD viva, with Prof. Andrew Weller (Oxford) as external examiner. Many congratulations!

13 March 2014: Francesco Zaccaria is joining us as a visiting Masters student for 3 months. He is an Erasmus student from Vincenzo Busico’s group at the University of Naples. Francesco’s project is the synthesis of a number of zirconium alkyl complexes with chelating ligands and the exploration of their behaviour as olefin polymerisation catalysts. Welcome to a comparatively mild and Italian-looking Norwich!

1 March 2014: Alexander Romanov joins the group from the Nesmeyanov Institute in Moscow. Alexander has ample experience in synthetic inorganic chemistry, in particular carborane and tripledecker complexes, including spectroelectrochemistry and crystal structure determinations. He is a recipient of the prestigious Y. T. Struchkov Award and has had a number of collaborations with the US and Mexico. He will lead the “outreach” type aspects of our research.

Alexander Romanov photo

1 February 2014: Julio Fernandez-Cestau from the University of Rioja joins the group as the first of several postdocs funded by the ERC project. Welcome to a chilly East Anglia! Julio is a very experienced postdoc and has worked primarily on the synthesis of photoactive platinum metal complexes, particularly acetylides and the synthesis and characterisation of photoluminescent materials.

Julio Fernandez-Cestau

January 2014: Dragoş Roşcais Fabio Ghiotto’s replacement on the EU project “MAO-Robots” project. His task will be the synthesis and characterisation of analogues of MAO, and their assessment under polymerisation conditions. Dragoş is keen on a change from gold chemistry and wants to broaden his chemical experience, so flammable aluminium alkyls are just the thing.

28-29 September 2013: Chrisa Pateraki attends a meeting in Brussels of your EU consortium on the structure and function of methylaluminoxane (MAO) and gives a presentation on her work to an audience of academics and industrialists.

23-24 September 2013: Dragoş has been shortlisted for the prestigious international Reaxys PhD Prize 2013 and invited give a presentation at the prize winners’ meeting at Grindelwald, Switzerland. He is one of 40 shortlisted candidates from over 500 applications.

September 2013: In collaboration with Greg Wildgoose’s group the bond dissociation energy of an unbridged Au(II)-Au(II) dimer has been determined. The paper has just been accepted.

22 August 2013: It’s farewell to Fabio Ghiotto, who is leaving the group to take up a permanent position in the finance department of British Airways. Good-bye Norwich, hello Slough! This was duly celebrated with lunch at the Rushcutters. Best wishes to Fabio and Antonella and good luck with the job and your future.

Photo of Fabio

27 July 2013: The ERC announced the award of an Advanced Grant for our project GOCAT: Gold(III) Chemistry: Structures, Bonding, Reactivity and Catalysis. This will secure funding for our gold chemistry for the next five years.

26 July 2013: Northern England Postgraduate Chemistry Conference, University of York. Dragoş at has been invited to give a talk at this meeting on his gold chemistry.

8 July 2013: School of Chemistry Research Day. Dragoş wins the School of Chemistry Prize for the best oral contribution and the highest scientific achievements in a PhD thesis. Many congratulations!

4-5 July 2013: Dalton Discussion Group meeting at Imperial College. Dragoş is representing our group at this meeting with an invited lecture on his gold(III) hydrides, oxides and peroxides.

Image of molecules

March 2013: Chiranjib Banerjee has successfully defended his thesis with flying colours on 26 March. Many congratulations! Chiranjib’s thesis work concerned the synthesis of indium phosphide nanowires and the construction of cadmium selenide conjugates with sub-phthalocyanine macrocycles, where he was able to show that 1:1 assemblies are formed. Chiranjib was co-supervised first by Professor Thomas Nann, and after his move to Australia by Yimin Chao and Andrew Cammidge. He has now returned to India and is continuing his research in nanoscience.  

   

January 2013: Ángel Bajo- Sánchez joined the group as a PhD student in January 2013. He obtained a Master Degree in Homogeneous Catalysis at the University of Castilla-La Mancha, Ciudad Real, under the supervision of Prof. Antonio Otero and Dr Rosa Paris. He has now started a project synthesizing new types of gold chelate complexes.

Dragoş Roşca and Nicky Savjani have prepared the first examples of gold(III) hydride and olefin complexes. The synthesis of Au(III) olefin complexes follows some 185 years after the report of the isoelectronic Pt(II) compound, Zeise’s salt. Their results have featured in an enthusiastic Highlight article in Angewandte Chemie and been given top billing in the annual review of inorganic chemistry in the Nachrichten aus der Chemie, the journal of the German Chemical Society:

A.S.K. Hashmi, „Fire and Ice“,
Angew. Chem. Int. Ed. 2012, 51, 12935.
R. Wolf, G. Clever, “Trend Reports: Highlights in Inorganic Chemistry 2012”
Nachr. Chem. 2013, 61, 235.

      

November 2012: Nicky Savjani has completed his PhD and viva in November 2012 with excellent results.

Nicky was co-supervised by Sean Bew. He worked on various topics in gold chemistry, including the C-H activations by Au+ which gave very nice kinetics and the synthesis of luminescent gold(I) clusters. He finished off with the successful synthesis of gold(III) norbornene and ethylene complexes. Nicky has now moved to Manchester University to a postdoc position in nano chemistry with Paul O’Brien.

Glowing gold clusters:

October 2012: Fabio Ghiotto and Chrisa Pateraki have won the prize for the poster with the best scientific content at the Chemelot2012 conference in Maastricht.

The Chemelot conferences are industrial invitation-only conferences, sponsored and organised by a conglomerate of multinational polyolefins and polymer producers, DSM, SABIC and Lanxess. This year’s conference celebrated 50 years of polyolefin production on the companies’ site near Maastricht in the Netherlands.

Fabio and Chrisa are working on an EU-funded project, “MAO-Robots”, a 3.3M Euro collaboration between the Research Centre Juelich (neutron scattering), the University of Eastern Finland (computational modelling), UEA (chemical understanding) and the industrial partners SABIC, DSM, Lanxess and Chemtura Organometallics GmbH, funded by the EU under the FP7 “Nanosciences, Nanotechnologies, Materials and new Production Technologies” call.  

February 2012: Dan Smith and Dragoş Roşca synthesize luminescent gold(III) pincer complexes which emit light from yellow to blue:

   

D.-A. Roşca, D. A. Smith, M. Bochmann, Chem. Commun. 2012, 48, 7247; D. A. Smith, D.-A. Roşca, M. Bochmann, Organometallics 2012, 31, 5988. Dan is a Leverhulme Trust postdoctoral fellow. In July 2012 he moved to Robin Perutz’ group in York.   

 

Research Projects

Olefin Polymerisation Catalysis and Catalyst Activation

The development of well-defined polymerisation catalysts, in particular those based on Group 4 metal complexes, ranks as one of the most prominent achievements of organometallic chemistry over the last 20 years. Polyolefin production worldwide is of the order of 108 metric tons per year. Polyolefins have become indispensable to modern society, they are light, eminently versatile in their materials properties, they are in principle fully recyclable, and can be manufactured with minimal waste. 

Organometallic catalysts are particularly attractive for polyolefin production: their ligand structures can be easily modified, and catalyst activation and dynamics can be readily controlled. Used imaginatively, these aspects are key to new materials and applications.

We are interested in the activation chemistry of these catalysts. Activation of polymerization catalysts consists of generating an equilibrium concentration of a coordinatively unsaturated species, usually cationic, that contains a reactive metal-alkyl bond and is capable of binding an olefin in such a manner that transfer of the alkyl ligand to the monomer can occur: 

In past work we have concentrated on activation by strong Lewis acids that form large, extremely weakly coordinating anions.1-3 Current research focuses on catalyst activation by the industrially preferred activator, methylaluminoxane (MAO). MAO is a complex substance of unknown structure, produced by the controlled hydrolysis of AlMe3. This research is part of an EU-funded consortium including the Research Centre Jülich, the industrial partners DSM, SABIC, Lanxess and Chemtura Organometallics GmbH, as well as the University of Eastern Finland, and is a multidisciplinary approach including organometallic synthesis and reaction kinetics (UEA), neutron scattering (Jülich), and computational modeling (Finland).

Our research combines NMR spectroscopic studies with the synthesis of MAO modifiers. We have developed methods for the rapid assessment of catalysts and activators by kinetic techniques which allows the simultaneous measurement of catalyst activity, the concentration of catalytically active sites, and the time dependence of the polymer molecular weight. The project is also trying to unravel which structural features in MAO are responsible for catalyst activation.

One of the results is that by controlling activator structure it is possible to “dial in” the polymer molecular weight.

Objective

This project aims at the elucidation of the “active ingredient” in a class of industrially highly important catalyst activators, using a multidisciplinary approach. It combines organometallic chemistry with various spectroscopic and computational methods, aimed at providing a rational strategy for the optimization of catalyst activators. 

Figure 1: Mechanism of the activation of the catalyst precursor Cp2TiCl2 by MAO, elucidated by NMR spectroscopy and isotopic labelling.

Figure 2: Time dependence of polymer molecular weight as a function of the grade and quality of the MAO catalyst activator.


Figure 3: Dependence of polymer molecular weight on the MAO composition.

Reviews:

(1) The Chemistry of Catalyst Activation: The Case of Group 4 Polymerization Catalysts. M. Bochmann, Organometallics 2010, 29, 4711 – 4740. 


(2) Kinetic and Mechanistic Aspects of Metallocene Polymerisation Catalysts. M. Bochmann, J. Organomet. Chem. 2004, 689, 3982-3998.

(3) Cationic Group IV Metallocene Complexes and Their Role in Polymerisation Catalysis: The Chemistry of Well-defined Ziegler Catalysts. M. Bochmann, J. Chem. Soc., Dalton Trans. 1996, 255 – 270.

 

Gold Chemistry: Catalytic intermediates and photoluminescent materials

Gold used to be considered as too inert to be of relevance to catalysis. We now know that this is not the case, and citations on the Web of Science to the term “gold catalyst” have risen from fewer than 20 in 1983 to over 38,000 in 2011. Nevertheless, key intermediates of catalytic cycles that for other noble metals were established decades ago were only recently found for gold. The reactivity of these intermediates is still largely unknown. 


Gold has a strongly positive oxidation potential and as such is much more easily reduced than neighbouring elements of catalytic interest such as platinum, palladium or rhodium. It might therefore be expected that Au(I) and Au(III) are readily reduced by hydride sources. However, with suitable choice of ligands this can be avoided, as shown by our recent synthesis of the first Au(III) hydride:1 

Figure 1. Synthesis and structure of the first isolable Au(III) hydride, (C^N^C)AuH.1 

See also:

  • Highlight Article in Angewandte Chemie (A.S.K. Hashmi, Angew. Chem. Int. Ed. 2012, 51, 12935);
  • Trend Reports: Highlights in Inorganic Chemistry 2012 (R. Wolf, G. Clever, Nachr. Chem. 2013, 61, 235).

Most unusually, this hydride can also be formed by O-abstraction for the hydroxide – an unprecedented reaction pathway. This reaction is relevant in the context of the M+ catalysed splitting of water and is being investigated by kinetics and isotopic labelling:


Figure 2: Conversion of Au-OH into Au-H (left), and the water splitting cycle (right).

Another class of fundamentally important but previously unknown compounds are gold(III) alkene complexes – such complexes are involved in most Au(III) mediated organic transformations but could never be isolated. This has now been achieved:2


Figure 3. Synthesis of the first examples of Au(III) olefin complexes. 

Gold complexes of pincer ligands – here the dianionic C^N^C pincer - have a rich chemistry. They are for example attractive as photoluminescent materials:3-5 
 

Figure 4. Variation of photoemission wavelengths of Au(III) aryls.3 

This project is concerned with:
(1) the synthesis of new, unprecedented types of Au(III) hydrides and the exploration of their insertion reactions and reactivity towards unsaturated substrates.
(2) Structure and bonding of gold pincer complexes. This includes for example new Au(II) complexes, as well as Au(III) carbonyls and new ligand systems. We collaborate with colleagues concerning the electrochemistry and computational modelling of the new complexes in order to understand what is so special about gold complexes.
(3) The synthesis of Au(III) pincer complexes with different ligand types, for applications as photoemitting materials and as potential anti-cancer agents. 

Figure 5. Structure of an Au(II) pincer complex.1 The compound is resistant to disproportionation but shows an interesting electrochemistry. 

References:

(1) A Thermally Stable Gold(III) Hydride: Synthesis, Reactivity, and Reductive Condensation as a new Route to AuII Complexes. D.-A. Roşca, D. A. Smith, M. Bochmann, Angew. Chem. Int. Ed. 2012, 51, 10643 –10646. 

(2) Gold(III) Olefin Complexes. N. Savjani, D.-A. Ro#015fca, M. Schormann, M. Bochmann, Angew. Chem. 2013, 125, 908 –911; Angew. Chem. Int. Ed. 2013, 52, 874 –877. DOI: 10.1002/anie.201208356.

(3) Cyclometallated Gold(III) Hydroxides as Versatile Synthons for Au-N, Au-C Complexes and Luminescent Compounds, D.-A.  Roşca, D. A. Smith, M. Bochmann, Chem. Commun. 2012, 48, 7247 – 7249.

(4) Synthesis and Structure, and Luminescent Behavior of Anionic Oligomeric and Polymeric Ag2Au2 clusters. N. Savjani, L. A. Wilkinson, D. L. Hughes, M. Bochmann, Organometallics 2012, 31, 7600–7609.

(5) Selective Au-C Cleavage in (C^N^C)Au(III) Aryl and Alkyl Pincer Complexes
D. A. Smith, D.-A.  Roşca, M. Bochmann, Organometallics 2012, 31, 5988 - 6000.

The Reactivity of “Ligand-free” Au+: C-H and C-C Activation versus ?-Coordination.
N. Savjani, S. Bew, D. L. Hughes, S. J. Lancaster, M. Bochmann, Organometallics 2012, 31, 2534?2537.

(6) Structural Variation in Gold(I)-Chelate Systems: Synthesis of an Asymmetrically Bridged ?-Diketimido Complex of Gold. N. Savjani, M. Schormann, M. Bochmann, Polyhedron 2012, 38, 137 - 140.

(7) Syntheses and Structures of Fluorinated Diketiminato Complexes of Gold and Copper. N. Carrera-Aguado, N. Savjani, J. Simpson, D. L. Hughes , M. Bochmann, Dalton Trans. 2011,40, 1016 – 1019.

(8) Synthesis and Structures of Gold Perfluorophthalimido Complexes. N. Savjani, S. J. Lancaster, S. Bew, D. L. Hughes , M. Bochmann, Dalton Trans. 2011, 40, 1079 – 1090. 

External Activities and Indicators of Esteem

  • Fellow of the Royal Society of Chemistry since 1993
  • Vice-President, RSC Dalton Council. 1998-2001
  • Royal Society:  Industry Fellowships Panel 2011 - 2014

  • Royal Society:  Newton Advanced Fellowships Panel, 2015 - 

  • External Examiner for Undergraduate Degrees: University of Hull (1999 – 2002), Warwick (2003 – 2005), Cambridge (2009 – 2011), Manchester (2009 – 2011), Imperial College London (2014 – 2015).

  • Assessor for professorial appointments at the Universities of Colorado, Pennsylvania, Toronto, Hong Kong, Singapore, Jordan; Strasbourg “habilitation”; Rennes “habilitation”.

  • PhD examiner at: Imperial College, University of Oxford, Warwick, Durham; Loughborough, Bath; France: Lille, Rennes; Spain: Valladolid; Norway: Trondheim


Enterprise and Engagement activities

  • UK representative of EuCheMS (European Association for Chemical and Molecular Sciences), Division of Organometallic Chemistry, on behalf of the RSC, 2015 - present

  • Associate Editor of the ACS journal Organometallics - 2006 - 2015
  • Volume editor of Comprehensive Organometallic Chemistry III - 2007

Professional Activities

  • Associate Editor of the ACS journal Organometallic. 2006-present
  • Volume editor of Comprehensive Organometallic Chemistry III. 2007