Dr Joy H. Farnaby

Contact: j.farnaby@imperial.ac.uk; +44 (0) 207594 6752 and +447568181068 Memberships: Royal Society of Chemistry (354859) and American Chemical Society (30228985).

Employment: 2014-2017 Junior Research Fellow, Imperial College London, UK Mentor: Prof. Nick Long 2012-2014 Postdoctoral Scholar. University of Edinburgh, Edinburgh, UK

PI: Prof. Polly L. Arnold 2011-2012 Postdoctoral Scholar. University of California Irvine, Irvine, CA, USA

PI: Prof. William J. Evans 2010-2011 Postdoctoral Scholar. Yale University, New Haven, CT, USA PI: Prof. Nilay Hazari

Qualifications:

2006-2010 D.Phil. Organometallic Chemistry, University of Sussex, Brighton, UK Supervisor: Prof. F. Geoffrey N. Cloke, FRS

‘Mixed-sandwich Complexes of Low-Valent Uranium for the Reductive Activation of Small Molecules.’

2002-2006 MChem. Chemistry with European Studies (Proficiency in German), Upper Second Class Honours, University of Sussex, Brighton, UK Supervisor: Prof. F. Geoffrey N. Cloke, FRS

2004-2005 Erasmus Research Project. SFB 558/Metal-Substrate Interactions in Heterogeneous Catalysis, Ruhr-Universität Bochum, Germany

Professional Responsibilities:

Invited Seminars:

2012, Los Alamos National Laboratory, Los Alamos, USA: ‘Reduction of CO and CO2 by Trivalent Uranium and Divalent Rare Earth Complexes.’ 2009, University of Sussex, UK: ‘Uranium(III) Mixed-Sandwich Complexes for the Reductive Activation of Small Molecules.’ Reviewer: Organometallics. Teaching: 2014-2017 Imperial College London:

• Inorganic Chemistry Tutorials (1st Year) • Synthesis Laboratory (2nd Year) • Literature Reports (3rd Year) • MSci Projects (4th Year)

2013-2014 University of Edinburgh: • 2 tutorial groups of 10-15 students (General Chemistry).

2006-2010 University of Sussex: • Convenor of Associate Tutor training workshop for post-graduate students. • Associate Tutor for undergraduate (Inorganic, Organometallic) and pre-med

(Organic/General Chemistry) laboratory courses. Responsibilities included design of the advanced organometallic laboratory course and marking scripts.

Dr Joy H. Farnaby

Supervision: 2014-2017 PhD student, Imperial College London. 2014-2015 MSci project student, Imperial College London. Mentoring and project supervision, including project design, of over 15 students (undergraduate, MChem and PhD) in the last 8 years. Collaborations: Prof. K. Meyer, Friedrich-Alexander University, Erlangen-Nuremberg, Germany Prof. F. Kraus, Philipps University, Marburg, Germany Prof. W. J. Evans, University of California Irvine, USA Prof. F. G. N. Cloke, University of Sussex, UK

Grants and awards: 2014:

• DTP PhD Studentship, Imperial College London. • Junior Research Fellowship, Imperial College London.

2013: • Actinide User Lab AUL-2013-15 Funded Project with Prof. Arnold: ‘Covalency and

magnetism studies of metal-metal interactions in dinuclear neptunium and heterobimetallic neptunium and uranium complexes.’

• Fellowship from the Technische Universität Munich to attend ‘Research Opportunities Week.’

• Travel grant from Karlsrühe Institute of Technology Programm NUKLEAR to attend ‘Actindes13’, Karlsrühe, Germany.

• Winner of Poster Prize at Actinides13. 2012:

• Travel grant from LANL Centre for Non-Linear Studies to attend ‘The Chemistry and Physics of the Heavy Elements,’ Santa Fe, USA. Publications:

8 publications in the last 2 years in high-impact, internationally recognized peer-reviewed journals. See appendix for complete list. Selected Publications: 10. ‘New Chemistry from an Old Reagent: Mono- and Dinuclear Macrocyclic Uranium(III) Complexes from [U(BH4)3(THF)2].’ Arnold, P. L.; Stevens, C. J. ‡; Farnaby, J. H. ‡; Gardiner, M. G.; Love, J. B. J. Am. Chem. Soc. 2014, 136, 10218-10221. ‡Equal contribution 9. ‘Switchable π-coordination and C-H metallation in small-cavity macrocyclic thorium and uranium complexes.’ Arnold, P. L.; Farnaby, J. H.; White, R. C.; Kaltsoyannis, N.; Gardiner, M. G.; Love, J. B. Chem. Sci. 2014, 5, 756-765. 6. ‘Expanding Yttrium Bis(trimethylsilylamide) Chemistry via the Reaction Chemistry of (N2)2-, (N2)3-, and (NO)2- Complexes.’ Farnaby, J. H.; Fang, M.; Ziller, J. W.; Evans, W. J., Inorg. Chem. 2012, 51, 11168-11176. 4. ‘Isolation of (CO)1- and (CO2)1- Radical Complexes of Rare Earths via Ln(NR2)3/K Reduction and [K2(18-crown-6)2]2+ Oligomerization.’ Fang, M.; Farnaby, J. H.; Ziller, J. W.; Bates, J. E.; Furche, F.; Evans, W. J. J. Am. Chem. Soc. 2012, 134, 6064-6067.

Letters of support available on request

Dr Joy H. Farnaby Appendix

Scientific Summary: DPhil: Mixed-sandwich complexes of Low-Valent Uranium for the Reductive Activation of Small Molecules My thesis examined the reactivity of [U(η8-C8H6{SiiPr3-1,4}2)(η5-CpR)(THF)] (R = CpMe5, CpMe4H) with small molecules and included the successful chemical abstraction of the labelled oxocarbon. The substitution of the monoanionic and dianionic ligands in the U(III) mixed-sandwich framework, led to the synthesis of [U(κ3-TpMe2)(η8-C8H6{SiiPr3-1,4}2)] and [U(κ3-TpMe2)(η8-C8H4{SiiPr3-1,4}2)] and

[U(η5-IndR)(η8-C8H6{SiiPr3-1,4}2)] (R = Me6, Me7). The reactivity of methylated indenyl complexes with carbon oxides was found to be complementary to the (CpR)- system but under different kinetic control and included the observation of the long-lived carbonyl complex [U(η5-IndMe7)(η8-C8H6{SiiPr3-1,4}2)(CO)] and the second example of the reductive tetramerisation of CO to the squarate dianion, (C4O4)2- (A), which was the first example of the extension of the reductive coupling of CO to other ligand systems. PDRA Yale: Bidentate N-heterocyclic carbenes in transition metal catalysis.

My project involved the synthesis of novel flexible bidentate amine-NHC ligands, with easily tuneable steric and electronic properties for transition metal catalysis. Complexation to Pd resulted in monomeric exclusively trans-NHC species, active catalysts for Suzuki and Heck reactions. In contrast the Rh and Ir species (active catalysts for both olefin and transfer hydrogenation), were isolated as NHC-bridged dimers, with axial chirality around the

M-Carbene bond. My most significant contribution to the group was to develop the synthetic methodology, which led to the successful synthesis of four novel and very unusual Fe(II) NHC complexes (B). PDRA UCI: Lanthanide radical chemistry and the first example of Lu2+

I was involved in a project that successfully isolated very rare (CO)1- and (CO2)1- radical species from the in situ generation of divalent rare earths, my contribution to this work was the extension of the chemistry from Y to Lu, which represented the first example of Lu2+. My independent project looked at expanding the reaction chemistry of the (N2)2-, (N2)3- and (NO)2- complexes based on the [(R2N)2(THF)Y]+ cation (R = SiMe3). The highlight of which was the isolation in high yield of the peroxide complex [(R2N)2(THF)Y]2(μ–η2:η2–O2) (C), which had long been a target of the Evans group. PDRA Edinburgh: Arene-Actinide interactions in the Flexible

Macrocyclic Ligand Environment of trans-Calix[2]benzene[2]pyrrolide Use of the small-cavity dianionic macrocycle (L)2- has enabled the successful synthesis of new U(IV) and U(III) species. The reduction of [UIV(L)I2] resulted in the isolation of the UIII species [U(L)I(THF)] and a switch in binding mode from κ5:κ5 to η6:κ1:η6:κ1 showing a preference for π-arene binding in the UIII species. The synthesis from uranium(III) starting materials led to the isolation of the very unusual dinuclear species [U2

IIII4(L)] (D) in which (L)2- bridges two [UIIII2]+ units in both binding modes. The conformational flexibility and switchable π-coordination of this macrocyclic ligand provides a unique and well-defined molecular environment in which to study the interaction of

low-valent uranium with arenes. Subsequent work is in progress to understand the electronic nature of the π-interactions and to explore the reactivity of the UIII complexes.

!

B

U (C4O4)

2-

U

A

Y

C

(O2)2-

Y

N1

U1 I3

N2

I2 U2

I1

D

Dr Joy H. Farnaby Appendix

i) Refereed papers in primary journals (* corresponding authors): 2014 10. P. L. Arnold,* C. J. Stevens,‡ J. H. Farnaby,‡ M. G. Gardiner and J. B. Love* (‡equal contribution) ‘New Chemistry from an Old Reagent: Mono- and Dinuclear Macrocyclic Uranium(III) Complexes from [U(BH4)3(THF)2].’ J. Am. Chem. Soc. 2014, 136, 10218-10221. 9. P. L. Arnold,* J. H. Farnaby, R. C. White, N. Kaltsoyannis,* M.G. Gardiner* and J. B. Love* ‘Switchable π-coordination and C-H metallation in small-cavity macrocyclic thorium and uranium complexes.’ Chem. Sci. 2014, 5, 756-765. 2013 8. S. M. Mansell, J. H. Farnaby, A. I. Gemeroth and P. L. Arnold* ‘A Thermally Stable Uranium Dinitrogen Complex with Siloxide Supporting Ligands.’ Organometallics, 2013, 32, 4214-4222. 7. J. Wu, W. Dai, J. H. Farnaby, N. Hazari,* J. J. Le Roy, V. Mereacre, M. Murugesu, A. K. Powell and M. K. Takase ‘Synthesis and Catalytic Activity of Iron Complexes with Bidentate NHC Ligands.’. Dalton Trans. 2013, 42, 7404-7413. 2012 6. J. H. Farnaby, M. Fang, J. W. Ziller and W. J. Evans* ‘Expanding Yttrium Bis(trimethylsilylamide) Chemistry via the Reaction Chemistry of (N2)2-, (N2)3-, and (NO)2- Complexes.’ Inorg. Chem. 2012, 51, 11168-11176. 5. J. F. Corbey, J. H. Farnaby, J. E. Bates, J. W. Ziller, F. Furche* and W. J. Evans* ‘Varying the Lewis Base Coordination of the Y2N2 Core in the Reduced Dinitrogen Complexes {[(Me3Si)2N]2(L)Y}2(µ-η2:η2-N2) (L = Benzonitrile, Pyridines, Triphenylphosphine Oxide, and Trimethylamine N-Oxide).’ Inorg. Chem. 2012, 51, 7867-7874. 4. M. Fang, J. H. Farnaby, J. W. Ziller, J. E. Bates, F. Furche* and W. J. Evans* ‘Isolation of (CO)1- and (CO2)1- Radical Complexes of Rare Earths via Ln(NR2)3/K Reduction and [K2(18-crown-6)2]2+ Oligomerization.’ J. Am. Chem. Soc. 2012, 134, 6064-6067. 3. J. M. Ashley, J. H. Farnaby, N. Hazari,* K. E. Kim, E. D. Luzik Jr., R. J. Meehan, E. B. Meyer, N. D. Schley, T. J. Schmeier and A. N. Tailor. 'Axially Chiral Dimeric Ir and Rh Complexes Bridged by Flexible NHC Ligands.’ Inorg. Chim. Acta 2012, 380, 399-410. Invited Article for Special Edition: Young Investigator Award 2011 2. J. D. Blakemore, M.J. Chalkley, J. H. Farnaby, L. M. Guard, N. Hazari,* C. D. Incarvito, E. D. Luzik Jr. and H. W. Suh ‘New Bidentate Trans-Chelating N-Heterocyclic Carbene Ligands for Palladium.’ Organometallics 2011, 30, 1818-1829. 2010 1. J. H. Farnaby, F. G. N. Cloke,* M. P. Coles, J. C. Green* and G. Aitken 'Tris(pyrazolyl)borate half-sandwich complexes of trivalent uranium incorporating the [C8H6{SiiPr3-1,4}2]2- and [C8H4{SiiPr3-1,4}2]2- ligands.’ Compt. Rend. Chimie 2010, 13, 812-820. Invited Article for Special Issue: ‘The Vitality of the Coordination Chemistry of the F-elements.’

Dr Joy H. Farnaby Appendix

ii) Symposia contributions: 2014 Oral presentation: J. H. Farnaby, N. Kaltsoyannis, M. G. Gardiner, J. B. Love and P. L. Arnold ‘trans-Calix[2]benzene[2]pyrrolide: A Flexible Macrocyclic Ligand For F-block Chemistry’ 3rd Meeting of the European F-Element Network, Nürnberg, Germany Poster presentations: J. H. Farnaby, M. G. Gardiner, J. B. Love and P. L. Arnold ‘The Chemistry of Low Oxidation State Uranium in a Flexible Macrocyclic Ligand Environment’ Dalton Discussion 14, Advancing the Chemistry of the F-elements, Edinburgh, UK and 9th Anglo-German Inorganic Chemistry, Edinburgh, UK. 2013 Poster presentations: J. H. Farnaby, N. Kaltsoyannis, M. G. Gardiner, J. B. Love and P. L. Arnold ‘Arene-Actinide interactions in the Flexible Macrocyclic Ligand Environment of trans-Calix[2]benzene[2]pyrrolide.’ Actinides 13, Karlsruhe, Germany (poster prize winner) and Irène Joliot-Curie, London, UK Poster presentation: J. H. Farnaby and P. L. Arnold ‘Making and Breaking Inert Bonds with Uranium Complexes’ 2nd Nuclear Academics Discussion Meeting, Birmingham, UK 2012 Invited oral presentation: J. H. Farnaby, W. J. Evans and F. G. N. Cloke ‘Reduction of CO and CO2 by Trivalent Uranium and Divalent Rare Earth Complexes.’ Los Alamos National Laboratory, Los Alamos, USA. Oral presentation: J. H. Farnaby, M. Fang, J. W. Ziller and W. J. Evans ‘Exploring the Reaction Chemistry of the Y[N(SiMe3)2]3/K Reduction System.’ 243rd ACS National Meeting, San Diego, USA. Poster presentation: J. H. Farnaby, M. Fang, J. W. Ziller and W. J. Evans ‘Reduction and Insertion Chemistry Generated by the Y[N(SiMe3)2]3/K System.’ Chemistry and Physics of the Heavy Elements, Santa Fe, USA. 2005-2009 Oral presentations: J. H. Farnaby and F. G. N. Cloke ‘Uranium(III) Mixed-Sandwich Complexes for the Reductive Activation of Small Molecules.’ Sussex Chemistry Seminar Series 2009, Brighton, UK and Postgraduate Synthesis Symposium 2008, Southampton, UK. Poster presentation: J. H. Farnaby and F. G. N. Cloke ‘Novel Mixed Sandwich Complexes of Uranium(III): Tp* vs. Cp*.’ 4th European Postgraduate Royal Society of Chemistry Industry Study Tour 2007, Germany and UK. Poster presentation: L. Khodier, E. Löffler, K. Kotsis, K. Fink, M. Moreno, J. H. Farnaby, K. Merz, M. Driess and M. Muhler. ‘IR spectroscopic and theoretical studies on molecular models of ZnO systems for methanol synthesis.’ 89th International Bunsen Discussion Meeting 2005, Meschede, Germany.