Currently the Mulvey group is developing the special synergistic chemistry that can be created through combining distinct components (mixtures of different metals and different ligands) within the same molecular environment. Fundamentally it could be said that mixing two distinct metal compounds, for example a lithium amide and a magnesium bisalkyl, produces a heterometallic molecule which acts neither as a lithium nor a magnesium compound but a compound of a unique new metallic element! Novel chemistry, beyond the scope of conventional homometallic reagents, is the reward. This idea has been applied to metallation chemistry. Metallation (transforming inert C-H bonds to reactive, useful C-Metal bonds) is one of the most important bond-making tools in chemistry, used routinely in synthetic laboratories worldwide, and increasingly employed from milligram to ton scales in fine chemical and pharmaceutical manufacture. In alkali-metal-mediated metallation the alkali metal is the catalyst while the formally less reactive metal (for example, magnesium or zinc) executes the deprotonation (low polarity metallation). Major challenges are to turn stoichiometric metallation reactions into catalytic processes and to invent ways of achieving unusual regioselectivities across a broad range of substrates.
For full free access to the latest paper on his synergistic mixed-metal research done in collaboration with Dr O’Hara and published in the journal Science (on14 November 2014, Issue 6211, Vol. 346, Pages 834-837) please use the links below.
Full Text: http://www.sciencemag.org/cgi/content/full/346/6211/834?ijkey=kaWzHVOzgowEk&keytype=ref&siteid=sci
Robert Emmet Mulvey was born in Glasgow, Scotland in 1959. He received his first degree (BSc. in Chemistry with 1st class Honours) and his Ph.D. (in organolithium chemistry under the direction of Dr Ron Snaith) at the University of Strathclyde in 1981 and 1984 respectively. Following two years as a postdoctoral fellow at the University of Durham (in the group of Professor Ken Wade), he returned to Strathclyde in 1986 and was promoted to a Professorship in 1995. To date he has published over 250 research papers and several book chapters. Exceeding £3M in total as PI, his career research income includes over £2.1M from EPSRC. A Fellow of the Royal Society of Edinburgh (FRSE), his research on polar organometallic chemistry has won him several awards and prizes as detailed below. Most recently his work was honoured by the GDCh Arfvedson Schlenk Prize for 2013, awarded for “outstanding achievements in discovering synergistic effects of mixed main group metal compositions”. Previously on the international advisory board of the ACS journal Organometallics, he joined the editorial board of Chemistry – A European Journal in 2014.
Prizes and awards
- Elected President of the Royal Society of Chemistry (RSC) Dalton Council
- Humboldt Research Award: One of Germany's most prestigious prizes for an international scholar
- Peking University, China - Eli Lilly Lectureship
- Elected member of RSC Dalton Council
- Arfvedson Schlenk Award 2013
- Royal Society Wolfson Merit Award
more prizes and awards
Selected Top Publications
1. “Synergic sedation of sensitive anions: alkali-mediated zincation of cyclic ethers and ethene”: A. R. Kennedy, J. Klett, R. E. Mulvey, D. S. Wright, Science, 2009, 326, 706. (This paper demonstrated that zinc reagents generally regarded to be poor bases can exhibit greatly enhanced deprotonating abilities when combined with sodium or potassium and that the sensitive ether or vinyl anions generated by such Zn-H exchanges can be stabilized through co-operative bimetallic bonding).
2. "Cleave and capture chemistry illustrated through bimetallic-induced fragmentation of tetrahydrofuran”: R. E. Mulvey, V. L. Blair, W. Clegg, A. R. Kennedy, J. Klett, L. Russo, Nature Chemistry, 2010, 2, 588. (Opposite to the “sedation” story in the Science paper, switching to a different bimetallic reagent leads to a catastrophic cleavage of THF, breaking 6 of its 13 bonds. All fragments are captured in novel crystalline bimetallic products).
3. “Regioselective tetrametalation of ferrocene in a single reaction: Extension of s-block inverse crown chemistry to the d-block” : W. Clegg, K. W. Henderson, A. R. Kennedy, R. E. Mulvey, C. T. O'Hara, R. B. Rowlings, D. M. Tooke, Angew. Chem. Int. Ed. 2001, 40, 3902–390. (Previously no known organomagnesium reagent could deprotonate a metallocene, but here using a synergic sodium-magnesiate reagent, ferrocene could be deprotonated not once but four times. The outcome of this remarkable regioselective tetramagnesiation was a new 16-membered inverse crown ring structure).
4. "Directed meta-metalation using alkali-metal-mediated zincation”: D. R. Armstrong, W. Clegg, S. H. Dale, E. Hevia, L. M. Hogg, G. W. Honeyman, R. E. Mulvey, Angew. Chem. Int. Ed. 2006, 45, 3775. (Metallation of substituted aromatic compounds usually occurs at the ortho position. Breaking this rule, this study reveals that deprotonation of anilines can be redirected to a meta site using a bimetallic reagent).
5. “Avante-garde metalating agents: structural basis of alkali-metal-mediated metalation”, R. E. Mulvey, Accounts of Chemical Research 2009, 42, 743. This perspective article summarises the achievements of the Mulvey group in synergic bimetallic chemistry over the past few years.
2011 Appointed to the 1919 Chair of Inorganic Chemistry, University of Strathclyde.
1995 Professor and Head of Inorganic Chemistry, University of Strathclyde.
1993 Senior Lecturer in Chemistry, University of Strathclyde.
1991 Lecturer in Chemistry, University of Strathclyde.
1986 Royal Society 1983 University Research Fellow, University of Strathclyde.
1984 Senior Research Assistant in Chemistry, University of Durham.
Awards and Fellowships
2013 Gesellschaft Deutscher Chemiker Arfvedson Schlenk Prize (2013): Awarded for “outstanding achievements in discovering synergistic effects of mixed main group metal compositions”.
2009-2014 Royal Society Wolfson Research Merit Award: Awarded for the study of “synergic mixed-metal chemistry: metallation and inverse crown applications”.
2004 Royal Society Leverhulme Trust Senior Research Fellowship: Awarded by the Royal Society for the study of “molecular synergy and inverse crown ring chemistry”.
2002 RSC Main Group Element Award: Given by the Royal Society of Chemistry for “elegant contributions to the metallo-organic and cluster chemistry of the alkali and alkaline earth metals”.
2001 Fellow of the Royal Society of Edinburgh: Elected to the Fellowship of the Royal Society of Edinburgh (FRSE).
1988 RSC Meldola Medal: Given by the Society of Maccabaeans and the Royal Society of Chemistry in respect of work on the synthesis and characterisation of the unprecedented species of lithium oligomer chemistry.
1986 Royal Society 1983 University Research Fellowship: Host institution, University of Strathclyde. Title of research project “Explorative coordination chemistries of Cu(I)/Zn(II) versus the alkaline/alkaline-earth metals”.
1984 The Ritchie Prize (1984): Given on the recommendation of the Chairman of the Department of Pure and Applied Chemistry, University of Strathclyde, to the PhD candidate “who presents the thesis which best combines excellence of scientific work with quality of presentation”.
- Outreach Presentation to Senior Pupils at St Aloysius' College, Glasgow
- Alkali Metal Organometallics: Masters of Mediation
- External PhD Examiner at University of Cambridge
- Outreach Presentation: A University Life
- Annual Meeting of the Alexander von Humboldt Foundation
- Alkali Metal Mediation in Synergistic Synthesis and Homogeneous Catalysis
more professional activities
- Propelling Sodium to the Forefront of Metallation Chemistry
- Mulvey, Robert (Principal Investigator) Robertson, Stuart (Co-investigator)
- 01-Jan-2020 - 31-Jan-2024
- Bespoke Bimetallics for Chemical Cooperativity
- Mulvey, Robert (Principal Investigator)
- 01-Jan-2019 - 31-Jan-2022
- Doctoral Training Partnership (DTP 2016-2017 University of Strathclyde) | Gauld, Richard Mackay
- Mulvey, Robert (Principal Investigator) Hevia, Eva (Co-investigator) Gauld, Richard Mackay (Research Co-investigator)
- 01-Jan-2016 - 01-Jan-2020
- Sodium Carboxylates in Diesel Fuels
- Mulvey, Robert (Principal Investigator)
- 01-Jan-2016 - 31-Jan-2020
- Towards a Paradigm Shift in the Principles and Practice of Polar Organometallic Chemistry
- Hevia, Eva (Principal Investigator) Mulvey, Robert (Co-investigator)
- "Polar organometallic chemistry provides an essential toolkit for transforming inert bonds into reactive bonds to make new compounds and materials. Very few aromatic molecules (e.g., pharmaceuticals, agrochemicals, perfumes) are made without polar organometallic chemistry being practiced at some stage in their manufacture. Though this chemistry has a long and successful history, it is currently at an exciting crossroads in its development with seemingly impossible challenges within it now on the verge of becoming possible. This project is designed towards fundamentally reforming the practice of polar organometallic chemistry making it more air and moisture compatible, greener, more atom-economical and sustainable. Research will focus on the synthesis, cultivation and exploitation of new s-block metal multicomponent reagents made by co-complexation protocols. Preliminary work has shown that mixing different components within the same environment (for example, two distinct metal complexes; or one metal but with an assortment of ligands) can lead to useful synergistic effects not possible with unmixed systems. The scope of the chemistry and the ability to construct new compounds and new materials to meet societal needs are thus greatly broadened.
Based on earth-abundant metals, these co-complex reagents will be screened in key organic transformations, focusing on deprotonative metallation and metal-halogen exchange reactions as well as in tandem C-C bond forming methods (as an alternative to more expensive and less environmentally benign transition-metal-mediated approaches) targeting synthetically relevant organic substrates. Stoichiometric reactions will be upgraded to catalytic regimes to establish the ground rules for s-block synergistic catalysis focusing on intramolecular hydroamination reactions of a range of unsaturated molecules.
A key objective of the project is to pioneer and extend the use of multicomponent polar organometallic reagents in Deep Eutectic Solvents (DESs). These DESs will provide more cost-effective, greener and biorenewable reaction media to those volatile organic solvents (VOC's) in which most polar organometallic chemistry is carried out today. Progress in this aim will go a long way to eventually realising the impossible challenge in polar organometallic chemistry of synthesising and utilising chemoselective organometallic reagents under air and/or in aqueous media. Dispensing with the need for a dry inert atmosphere would have genuine worldwide implications for the practice of polar organometallic chemistry both in academia and industry."
- 08-Jan-2015 - 07-Jan-2019
- Doctoral Training Partnership (DTP - University of Strathclyde) | Pollard, Victoria
- Mulvey, Robert (Principal Investigator) Hevia, Eva (Co-investigator) Pollard, Victoria (Research Co-investigator)
- 01-Jan-2015 - 10-Jan-2019
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