Staff Profile
Dr John Errington
Reader Metalorganic Chemistry
- Telephone: +44 (0) 191 208 6643
- Address: Chemistry
Bedson Building
School of Natural & Environmental Sciences
Newcastle University
NE1 7RU
Background
Research Interests
My interest in polyoxometalates and metal alkoxides includes their use as homogeneous catalysts, as models for and precursors to heterogeneous catalysts with well defined reactive sites and as nanoscale materials for energy conversion and storage. Our novel approaches to synthesis have enabled detailed systematic investigations of reactivity with extensive use of multinuclear NMR. 17O NMR in particular provides us with significant insight into mechanistic aspects.
Background
After obtaining my BSc in the School of Chemistry at Leeds University, I worked with Prof Bernard L. Shaw FRS for my PhD. The project involved the synthesis and reactivity of transition metal complexes of bulky phosphines and thioethers, particularly of alpha, omega-bis(di-t-butylphosphino)alkanes, and established the basis for what is now an expanding area of organometallic chemistry involving complexes of 'pincer ligands', as reviewed by Milstein in Chem. Rev, 2003, 103, 1759-1792. One notable result was the observation of rapid and reversible C–H bond cleavage under ambient conditions in a metalated Rh complex.
A postdoctoral position with Prof. Malcolm H. Chisholm FRS at Indiana University from November 1980 until December 1981 involved metal-metal multiply-bonded compounds of Mo and W and my work demonstrated that metal-metal bond coupling occurs when chloro, bromo or fluoro ligands replace isopropoxide groups in dinuclear triply-bonded Mo2(OPr)6.
I returned to the UK at the end of 1981 to work with Prof. Don Bradley FRS at Queen Mary College London from January 1982. After developing some organoimido chemistry of Group 6 transition metals I transferred to a project involving chemical vapour deposition of III/V semiconductor materials. During this inroduction to materials chemistry I demonstrated the use of di-t-butyl phosphine as a source of P in the CVD of InP. Around this time I also became interested in polyoxometalates and the possibility of replacing some (or all) of the surface oxygens with organoimido groups, although this would have to wait until I began work at Newcastle University in 1984.
I was appointed to a "New Blood" lectureship at Newcastle University in 1984 and began a programme to investigate the non-aqueous synthesis and reactivity of early transition metal polyoxoanions (polyoxometalates). This resulted in the development of routes to organoimido-substituted hexamolybdates and of hydrolytic routes to various mixed-metal hexametalates having reactive alkoxide sites. The chemistry of these nanoscale molecular metal oxides is now generating a great deal of interest and our polyoxometalate work has now extended to amphiphilic derivatives, surface immobilised species, electron-rich polyoxometalates and fundamental aspects of electron- and proton-transfer processes. I was Chair of the European COST Action “Polyoxometalate Chemistry for Molecular Nanoscience” (PoCheMoN, 2012-2016) and I am currently PI and leader of the EPSRC-JSPS Core-to-Core International Network on Polyoxometalate Science for Advanced Functional Energy Materials (INPOMS, 2019-2024 and UK representative in the CNRS Polyoxometalate International Research Network (2019-present).
Qualifications
BSc. Hons, PhD, CChem FRSC
Research
Research Interests
My interests lie at the interface between molecular solution chemistry and the solid state chemistry of oxide materials. As a consequence, our work centres around a wide range of metal complexes in which the metal is bonded to oxygen donor ligands, particularly polyoxometalates and metal alkoxides and their derivatives.
Other Expertise
Design and synthesis of molecular precursors for materials applications.
Current Work
Detailed multinuclear NMR studies of solution speciation in non-aqueous polyoxometalate chemistry.
Development of versatile, efficient and scaleable routes to reactive heterometal polyoxometalates for theoretical and catalysis studies.
Synthesis and reactivity of functionalised and electron-rich polyoxometalates as nanoscale building blocks and functional components of molecular assemblies.
Teaching
Undergraduate Teaching
In my time at Newcastle I have taught various aspects of Inorganic Chemistry to undergraduates at all stages including:
Transition metal chemistry
Organometallic chemistry
Applications of symmetry
Multinuclear NMR in structural chemistry
Catalyst Application and Design
Molecular Aspects of Materials Chemistry
Publications
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Articles
- Shiels D, Pascual-Borràs M, Waddell PG, Wills C, Poblet JM, Errington RJ. A thirty-year old mystery solved: identification of a new heptatungstate from non-aqueous solutions. Chemical Communications 2023, 59(51), 7919-7922.
- Iwano T, Shitamatsu K, Ogiwara N, Okuno M, Kikukawa Y, Ikemoto S, Shirai S, Muratsugu S, Waddell PG, Errington RJ, Sadakane M, Uchida S. Ultrahigh Proton Conduction via Extended Hydrogen-Bonding Network in a Preyssler-Type Polyoxometalate-Based Framework Functionalized with a Lanthanide Ion. ACS Applied Materials and Interfaces 2021, 13(16), 19138-19147.
- Shitamatsu K, Kojima T, Waddell PG, Sugiarto, Ooyama HE, Errington RJ, Sadakane M. Structural Characterization of Cerium-encapsulated Preyssler-type Phosphotungstate: Additional Evidence of Ce(III) in the Cavity. Zeitschrift fur Anorganische und Allgemeine Chemie 2021, 647(11), 1239-1244.
- Maksimchuk NV, Evtushok VY, Zalomaeva OV, Maksimov GM, Ivanchikova ID, Chesalov YA, Eltsov IV, Abramov PA, Glazneva TS, Yanshole YA, Kholdeeva OA, Errington RJ, Solé-Daura A, Poblet JM, Carbó JJ. Activation of H2O2 over Zr(IV). Insights from Model Studies on Zr-monosubstituted Lindqvist Tungstates. ACS Catalysis 2021, 11(16), 10589-10603.
- Di A, Schmitt J, Da Silva MA, Hossain KMZ, Mahmoudi N, Errington RJ, Edler KJ. Self-assembly of amphiphilic polyoxometalates for the preparation of mesoporous polyoxometalate-titania catalysts. Nanoscale 2020, 12(43), 22245-22257.
- Di A, Schmitt J, Ma K, da Silva MA, Elstone NS, Mahmoudi N, Li P, Washington A, Wang Z, Errington RJ, Edler KJ. Antagonistic mixing in micelles of amphiphilic polyoxometalates and hexaethylene glycol monododecyl ether. Journal of Colloid and Interface Science 2020, 578, 608-618.
- Maksimchuk NV, Ivanchikova ID, Maksimov GM, Eltsov IV, Evtushok VY, Kholdeeva OA, Lebbie D, Errington RJ, Solé-Daura A, Poblet JM, Carbó JJ. Why does Nb(V) show higher heterolytic pathway selectivity than Ti(IV) in epoxidation with H2O2? Answers from model studies on Nb- and Ti-substituted Lindqvist tungstates. ACS Catalysis 2019, 9, 6262-6275.
- Kandasamy B, Bruce PG, Clegg W, Harrington RW, Rodriguez-Fortea A, Pascual-Borras M, Errington RJ. Bonding insights from structural and spectroscopic comparisons of {SnW5} and {TiW5} alkoxido- and aryloxido-substituted Lindqvist polyoxometalates. Chemistry A European Journal 2018, 24(11), 2750-2757.
- Canioni R, Cadot E, Errington RJ, Leclerc-Laronze N, Roche-Marchal C. Synthesis, Structural and Electrochemical Properties of the [SbIII2SiMo12O40]4– anion, a Bicapped Keggin Polyoxometalate. Current Inorganic Chemistry 2017, 7(1), 13-20.
- Klonowski P, Goloboy JC, Uribe-Romo FJ, Sun FR, Zhu LY, Gandara F, Wills C, Errington RJ, Yaghi OM, Klemperer WG. Synthesis and Characterization of the Platinum-Substituted Keggin Anion α-H2SiPtW11O404-. Inorganic Chemistry 2014, 53(24), 13239-13246.
- Pascual-Borras M, Lopez X, Rodriguez-Fortea A, Errington RJ, Poblet JM. 17O NMR chemical shifts in oxometalates: from the simplest monometallic species to mixed-metal polyoxometalates. Chemical Science 2014, 5(5), 2031-2042.
- Long D-L, de la Oliva AR, Yan J, Busche C, Miras HN, Errington J, Cronin L. A redox-triggered structural rearrangement in an iodate-templated polyoxotungstate cluster cage. Chemical Communications 2013, 49(84), 9731-9733.
- Bakri R, Booth A, Harle G, Middleton PS, Wills C, Clegg W, Harrington RW, Errington RJ. Rational addition of capping groups to the phosphomolybdate Keggin anion [PMo12O40]3– by mild, non-aqueous reductive aggregation. Chemical Communications 2012, 48(22), 2779-2781.
- Coyle L, Middleton PS, Murphy CJ, Clegg W, Harrington RW, Errington RJ. Protonolysis of [(iPrO)TiMo5O18](3-): access to a family of TiMo5 Lindqvist type polyoxometalates. Dalton Transactions 2012, 41(3), 971-981.
- Kandasamy B, Wills C, McFarlane W, Clegg W, Harrington RW, Rodriguez-Fortea A, Poblet JM, Bruce PG, Errington RJ. An Alkoxido-Tin-Substituted Polyoxometalate [(MeO)SnW5O18](3-): The First Member of a New Family of Reactive {SnW5} Lindqvist-Type Anions. Chemistry: A European Journal 2012, 18(1), 59-62.
- Errington RJ, Coyle L, Middleton PS, Murphy CJ, Clegg W, Harrington RW. Synthesis and Structure of the Alkoxido-Titanium Pentamolybdate (nBu4N)3[(iPrO)TiMo5O18]: An Entry into Systematic TiMo5 Reactivity. Journal of Cluster Science 2010, 21(3), 503-514.
- Errington RJ, Harle G, Clegg W, Harrington RW. Extending the Lindqvist Family to Late 3d Transition Metals: A Rational Entry to CoW5 Hexametalate Chemistry. European Journal of Inorganic Chemistry 2009, 2009(34), 5240-5246.
- Errington RJ, Petkar SS, Middleton PS, McFarlane W, Clegg W, Coxall RA, Harrington RW. Synthesis and reactivity of the methoxozirconium pentatungstate ( nBu4N)6[{(μ-MeO)ZrW5O 18}2]: Insights into proton-transfer reactions, solution dynamics, and assembly of {ZrW5O18}2- building blocks. Journal of the American Chemical Society 2007, 129(40), 12181-12196.
- Errington RJ, Petkar SS, Middleton PS, McFarlane W, Clegg W, Coxall RA, Harrington RW. Non-aqueous synthetic methodology for TiW5 polyoxometalates: Protonolysis of [(MeO)TiW5O18]3- with alcohols, water and phenols. Dalton Transactions 2007, (44), 5211-5222.
- Clegg W, Elsegood MRJ, Errington RJ, Wingad RL. Bis(tetrabutylammonium) -oxalato-bis[dibromidodioxidotungstate(VI)]. Acta Crystallographica. Section E: Structure Reports Online 2007, 63(5), m1269-m1270.
- Kessler VG, Seisenbaeva GA, Errington RJ. The structural characterization of the first mononuclear alkoxide cation: Isolation and X-ray study of [Mo(OMe)5(CH3CN)]Bi 2Cl7. Inorganic Chemistry Communications 2005, 8(6), 503-505.
- Errington RJ, Petkar SS, Horrocks BR, Houlton A, Lie LH, Patole SN. Covalent immobilization of a TiW5 polyoxometalate on derivatized silicon surfaces. Angewandte Chemie - International Edition 2005, 44(8), 1254-1257.
- Doherty S, Errington RJ, Housley N, Clegg W. Dimeric aluminum chloride complexes of N-alkoxyalkyl-β-ketoimines: Activation with propylene oxide to form efficient lactide polymerization catalysts. Organometallics 2004, 23(10), 2382-2388.
- Tombul M, Errington RJ, Coxall RA, Clegg W. Tetrakis(μ3-phenoxo-acetonitrilelithium), a tetrameric lithium aryloxide with a cubane core. Acta Crystallographica Section E: Structure Reports Online 2003, 59(3), m137-m139.
- Errington RJ, Tombul M, Coxall RA, Clegg W. An alkoxide cluster with 18 Li+ ions encapsulating two borate anions, [tBuO)12Li18(BO3)2\]. Acta Crystallographica. Section C: Crystal Structure Communications 2003, 59(6), M231-M233.
- Tombul M, Errington RJ, Coxall RA, Clegg W. Tetrakis(mu-3-phenoxo-acetonitrilelithium), a tetrameric lithium aryloxide with a cubane core. Acta Crystallographica. Section E: Structure Reports Online 2002, E59(3), M137-M139.
- Errington RJ, Wingad RL, Clegg W, Elsegood MRJ. Direct bromination of Keggin fragments to give [PW9O28Br6]3-: A polyoxotungstate with a hexabrominated face. Angewandte Chemie - International Edition 2000, 39(21), 3884-3886.
- Errington RJ, Tombul M, Walker GLP, Clegg W, Heath SL, Horsburgh L. Tetraphenoxoborate complexes of barium: Crystal structures of the metalloborates [Ba(thf)4{B(OPh)4}2] and [Ba(dme)2{B(OPh)4}2]. Journal of the Chemical Society - Dalton Transactions 1999, (20), 3533-3534.
- Doherty S, Errington RJ, Housley N, Ridland J, Clegg W, Elsegood MRJ. N-alkoxy-beta-ketoiminate complexes of groups 4 and 5: Synthesis and characterization of the complexes [(eta(5)-C5H4R)M{CH3C(O)CHC(NCH2CHR ' O)CH3}Cl-n] (M = Ti, n = 1; M = Nb, n = 2; R = H, Me; R ' = H, Me), [Ti{CH3C(O)CHC(NCH2CHR ' O)CH3}Cl-2(thf)], and [Ti{CH3C(O)CHC(NCH2CHR ' O)CH3}(2)]. Organometallics 1999, 18(6), 1018-1029.
- Doherty S, Errington RJ, Jarvis AP, Collins S, Clegg W, Elsegood MRJ. Polymerization of ethylene by the electrophilic mixed cyclopentadienylpyridylalkoxide complexes [CpM{NC5H4(CR2O)-2}Cl2] (M = Ti, Zr, R = Ph, Pri). Organometallics 1998, 17(16), 3408-3410.
- Errington RJ, Ridland J, Sherwood JM, Clegg W. Beta-diketonate derivatives of titanium alkoxides: X-ray crystal structures and solution dynamics of the binuclear complexes [{Ti(OR)3(beta-dik)}2]. Polyhedron, 17, 659-674 1998.
- Errington RJ, Havelock J, Clegg W, Elsegood MRJ. Alkoxide hydrolysis as a route to early transition-metal polyoxometalates: Synthesis and crystal structures of heteronuclear hexametalate derivatives. Journal of the Chemical Society-Dalton Transactions, 5, 681-690 1996.
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Authored Book
- Errington R.J. Advanced Practical Inorganic and Metalorganic Chemistry. London: Blackie Academic & Professional, 1997.
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Book Chapters
- Errington RJ. Nonaqueous Polyoxometalate Synthesis for Systematic Studies of Hydrolysis, Protonation, and Reduction. In: Rudi van Eldik and Leroy Cronin, ed. Polyoxometalate Chemistry. Elsevier, 2017, pp.287-336.
- Errington RJ, Kandasamy B, Lebbie D, Izuagie T. Alkoxido-Derivatised Lindqvist and Keggin Type Polyoxometalates. In: Song, Y-F, ed. Polyoxometalate-Based Assemblies and Functional Materials. Springer, 2017, pp.1-25.
- Errington RJ. Structure of Oxo Metallic Clusters. In: McCleverty, J.A., Meyer, T.J, ed. Comprehensive Coordination Chemistry II: From Biology to Nanotechnology. Oxford, UK: Elsevier Science, 2003, pp.759-773.
- Errington RJ. Rational Approaches to Polyoxometalate Synthesis. In: Pope M.T., Müller A, ed. Polyoxometalate Chemistry: From Topology via Self-Assembly to Applications. Dordrecht: Springer, 2001, pp.7-22.
- Errington R.J, Richards D.G, Clegg W and Fraser K.A. New Aspects of Non-Aqueous Polyoxometalate Chemistry. In: Müller A. and Pope M.T, ed. Polyoxometalates: From Platonic Solids to Anti-Retroviral Activity. 1994, pp.105-114.
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Conference Proceedings (inc. Abstracts)
- Errington RJ, Petkar SS, Middleton PS. INOR 440-Protonolysis and related reactions of alkoxo-hexametalates [(RO)nM'xM6-xO19-n]z-: Insights into solution dynamics, steric effects and higher aggregation processes. In: Abstracts of Papers of the American Chemical Society. 2007, American Chemical Society.
- Errington RJ. General Strategies for Non-Aqueous Polyoxometalate Synthesis. In: Polyoxometalate Molecular Science: Proceedings of the NATO Advanced Study Institute. 2003, Tenerife, Spain: Springer.
- Errington RJ. General strategies for non-aqueous polyoxometalate synthesis. In: Polyoxometalate Molecular Science. 2003, Tenerife, Spain: Springer.
- Errington RJ, Walker GLP, Elsegood MRJ. The influence of ligands L-n on the structures of the new Group 2 metalloborates LnMB2(OPh)(8). In: Abstracts of Papers of the American Chemical Society. 1999, American Chemical Society.