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Personal Statement

Versatile virtuosi, organolithium reagents have been at the forefront of synthetic chemistry for over a century, as masters of mediation in chemical synthesis, for example, as brilliant bases, nucleophiles, or ligand transfer agents, making them indispensable in academia and technology. Today, this alkali metal mediation is expanding to the heavier congeners, sodium, potassium, rubidium and caesium with applications across a growing diversity of areas, covering not just stoichiometric reactions but remarkably also catalytic reactions in homogeneous catalysis. Alkali metals do not only mediate reactions on their own, they induce strong synergistic (co-operative) effects with metals from essentially the entire periodic table. These bimetallic systems often show reactivities or selectivities not possible with the second metal such as magnesium, zinc or aluminium, and operate to a different degree depending on which alkali metal is present.  

Two reviews from our group showcase the current state-of-the-art, while three of our primary papers report that surprisingly organocaesium compounds can outperform their lighter alkali metal congeners in catalytic transfer hydrogenation applications.

https://pubs.acs.org/doi/epdf/10.1021/acs.chemrev.9b00047?ref=article_openPDF

https://onlinelibrary.wiley.com/doi/epdf/10.1002/anie.202010963

https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/cctc.202100218

https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202400655

https://onlinelibrary.wiley.com/doi/epdf/10.1002/anie.202304966

Biography

Robert Emmet Mulvey was born in Easterhouse, Glasgow, Scotland in 1959.  He received his first degree (BSc. in Chemistry with First Class Honours) and his Ph.D. (in organolithium chemistry under the direction of his brilliant mentor 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.  33 students have obtained their PhD degrees in his group. To date he has published over 324 research papers and several book chapters. Exceeding £5M in total as PI, his career research income includes over £2.6M 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.  

Research Interests

Career History

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

President's Medal of the Royal Society of Chemistry (2023): Awarded for his immense contributions to the Dalton Division, especially his work supporting early career researchers.

Humboldt Research Award (2017): Awarded for “contributions to molecular inorganic chemistry”; Host; Prof. Dr. M. Scheer, Institut für Anorganische Chemie, Universität Regensburg, Germany.

PKU-Eli Lilly Lectureship (2015): Awarded for “creative and seminal research work in main group organometallic chemistry” by Peking University, Beijing, China.

Gesellschaft Deutscher Chemiker Arfvedson Schlenk Prize (2013): Awarded for “outstanding achievements in discovering synergistic effects of mixed main group metal compositions”.

Royal Society Wolfson Research Merit Award (2009-2014): Awarded for the study of “synergic mixed-metal chemistry: metallation and inverse crown applications”.

Royal Society Leverhulme Trust Senior Research Fellowship (2004): Awarded by the Royal Society for the study of “molecular synergy and inverse crown ring chemistry”.

RSC Main Group Element Award (2002): Given by the Royal Society of Chemistry for “elegant contributions to the metallo-organic and cluster chemistry of the alkali and alkaline earth metals”.

RSC Meldola Medal (1988): 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.

Royal Society 1983 University Research Fellowship (1986): Host institution, University of Strathclyde.  Title of research project “Explorative coordination chemistries of Cu(I)/Zn(II) versus the alkaline/alkaline-earth metals”.

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”.

Academic / Professional qualifications

2019-2022 President of the RSC Dalton Division Council.

2002 Fellow of the Royal Society of Chemistry (FRSC).

2001 Fellow of the Royal Society of Edinburgh (FRSE).

2001 Member of the Higher Education Academy.

2001 Member of the American Chemical Society.

1991 Member of the Royal Society of Chemistry (MRSC), Chartered Chemist (CChem).

1986 Graduate of the Royal Society of Chemistry (GRSC).

Selected Top Publications

1. T. X. Gentner, M. J. Evans, A. R. Kennedy, S. E. Neale, C. L. McMullin, M. P. Coles and R. E. Mulvey, Rubidium and caesium aluminyls: synthesis, structures and reactivity in C–H bond activation of benzene, Chem. Commun. 2022, 58, 1390.

Expanding knowledge of low valent aluminium chemistry, rubidium and caesium aluminyls are reported to complete the group 1 (Li–Cs) set of metal aluminyls. Citations (as of 29/1/25) 34.

2. T. X. Gentner, A. R. Kennedy, E. Hevia and R. E. Mulvey, Alkali metal (Li, Na, K, Rb, Cs) mediation in magnesium hexamethyldisilazide [Mg(HMDS)2] catalysed transfer hydrogenation of alkenes, ChemCatChem, 2021,13, 2371.

By screening all Group 1 metals (Li Cs), the efficiency of their catalyses gives an indication of the relative power of the synergistic effect exertedon magnesium by the alkali metal. The Cs Mg partnership shows the best efficiency with styrene, while K Mg works best with 1,1-diphenylethylene. Citations (as of 29/1/25) 33.

3. V. A. Pollard, A. Young, R. McLellan, A. R. Kennedy, T. Tuttle and R. E. Mulvey, Lithium-aluminate-catalyzed hydrophosphination applications, Angew. Chem. Int. Ed., 2019, 58, 12291.

Synthesized, isolated, and characterized by X-ray crystallography and NMR spectroscopic studies, lithium phosphidoaluminate iBu3AlPPh2Li(THF)3 has been tested as a catalyst for hydrophosphination of alkynes, alkenes, and carbodiimides. Citations (as of 29/1/25) 42.

 4.  V. A. Pollard, M. Ángeles Fuentes, A. R. Kennedy, R. McLellan and R. E. Mulvey, Comparing neutral (monometallic) and anionic (bimetallic) aluminum complexes in hydroboration catalysis: influences of lithium cooperation and ligand set. Angew. Chem. Int. Ed. 2018, 57, 10651. 

Bimetallic lithium aluminates and neutral aluminum counterparts are compared as catalysts in hydroboration reactions with aldehydes, ketones, imines and alkynes. Possessing Li–Al cooperativity, ate catalysts are found to be generally superior. Citaions (as of 29/1/25), 81.

5. A. J. Martínez-Martínez, A. R. Kennedy, R. E. Mulvey and C. T. O’Hara, Directed ortho-meta’- and meta-meta’-dimetalations: a template base approach to deprotonation, Science, 2014, 346, 834.

Here, we introduce a protocol by which the metalating agent, a disodium-monomagnesium alkyl-amide, forms a template that extends regioselectivity to more distant arene sites. Depending on the nature of the directing group, ortho-meta′ or meta-meta′ dimetalation is observed. Citations (as of 29/1/25) 163.

6. R. E. Mulvey, V. L. Blair, W. Clegg, A. R. Kennedy, J. Klett, L. Russo, Cleave and capture chemistry illustrated through bimetallic-induced fragmentation of tetrahydrofuran, Nature Chemistry, 2010, 2, 588.

 Opposite to the “sedation” story in the 2009 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. Citations (as of 29/1/25) 117.

7. A. R. Kennedy, J. Klett, R. E. Mulvey, D. S. Wright, Synergic sedation of sensitive anions: alkali-mediated zincation of cyclic ethers and ethene, Science, 2009, 326, 706.

This paper demonstrates 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. Citations (as of 29/1/25) 129.

8. R. E. Mulvey, F. Mongin, M. Uchiyama, Y. Kondo, Deprotonative metalation using ate compounds: Synergy, synthesis, and structure building, Angew. Chem. Int. Ed., 2007, 46, 3802.

This review reports that deprotonation accomplished by organometallic ate complexes has opened up new perspectives in organic chemistry with unprecedented reactivities and sometimes unusual and unpredictable regioselectivities. Citations (as of 29/1/25) 506.

9. D. R. Armstrong, W. Clegg, S. H. Dale, E. Hevia, L. M. Hogg, G. W. Honeyman, R. E. Mulvey, Directed meta-metalation using alkali-metal-mediated zincation, 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. Citations (as of 29/1/25) 95.

10.   W. Clegg, K. W. Henderson, A. R. Kennedy, R. E. Mulvey, C. T. O'Hara, R. B. Rowlings, D. M. Tooke,  Regioselective tetrametalation of ferrocene in a single reaction: Extension of s-block inverse crown chemistry to the d-block, Angew. Chem. Int. Ed. 2001, 40, 3902.  

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). Citations (as of 29/1/25) 112.

Expertise related to UN Sustainable Development Goals

In 2015, UN member states agreed to 17 global Sustainable Development Goals (SDGs) to end poverty, protect the planet and ensure prosperity for all. This person’s work contributes towards the following SDG(s):

  • SDG 7 - Affordable and Clean Energy
  • SDG 12 - Responsible Consumption and Production

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