Dr Anthony Haynes

School of Mathematical and Physical Sciences

Reader in Inorganic Chemistry

Anthony Haynes
Profile picture of Anthony Haynes
a.haynes@sheffield.ac.uk
Dainton Building

Full contact details

Dr Anthony Haynes
School of Mathematical and Physical Sciences
Dainton Building
13 Brook Hill
Sheffield
S3 7HF
Profile

Dr. Haynes obtained his BSc from the University of Exeter in 1986. After obtaining his PhD from the University of Nottingham in 1989, he became a BP Chemicals Research Fellow at the University of Sheffield until 1993, when he was appointed the BP Chemicals Lecturer in Homogeneous Catalysis.

In 1998 he was appointed as Lecturer at the University of Sheffield. From this post he was promoted to Senior Lecturer (2002) and Reader (2009).

Qualifications
  • MRSC
  • CChem
Research interests

The Haynes group investigates mechanistic aspects of homogeneous transition metal catalysed reactions, particularly industrially important processes such as methanol carbonylation and alkene hydroformylation. Synthetic, spectroscopic, kinetic and computational methods are used to study the structure and reactivity of organometallic complexes and their roles in catalysis.

Mechanisms of rhodium and iridium catalysed methanol carbonylation

The catalytic carbonylation of methanol to acetic acid is one of the most significant industrial applications of homogeneous transition metal catalysis. We have a long-standing research collaboration with BP Chemicals, who operate methanol carbonylation plants worldwide, and introduced a new process(Cativa TM) in 1995 that uses a promoted iridium/iodide catalyst. Highlights of our mechanistic studies include the first spectroscopic detection of a highly reactive Rh-methyl intermediate in the rhodium-catalysed process[1] and elucidation of the role of promoters in the iridium-based system.[2] We recently showed that the rate of migratory CO insertion in [Ir(CO)2I3Me]- is dramatically increased by isomerisation to place a CO ligand trans to methyl.[3]

Ligand effects on oxidative addition and migratory CO insertion

We are interested in how the rates of key steps in catalytic cycles can be influenced by the electronic and steric properties of "spectator" ligands, e.g. phosphines, imines and N-heterocyclic carbenes. Strongly donating ligands tend to promote oxidative addition and retard migratory CO insertion, whereas sterically bulky ligands tend to have the opposite effects on these steps.[4] In a recent study of the mechanism of rhodium/xantphos-catalysed methanol carbonylation it was found that the key intermediates contained xantphos coordinated as a tridentate "pincer" ligand and the nucleophilicity of the metal centre is enhanced by a Rh---O interaction.[5]

Computational studies

Our experimental studies are complimented by theoretical calculations, carried out in collaboration with Dr. Anthony Meijer in this department. We are interested in modelling trends in organometallic reactivity and spectroscopic properties, e.g. vibrational spectra of metal carbonyl complexes.

Facilities

The department is well-equipped with modern instrumentation for NMR spectroscopy, X-ray crystallography, mass-spectrometry and chromatography. In addition, the group has dedicated FTIR instruments for kinetic measurements, including high pressure and stopped-flow IR cells.

References

1. (a) JACS, 1991, 113, 8567; (b) JACS, 1993, 115, 4093.
2. JACS, 2004, 126, 2847.
3. Inorg. Chem., 2009, 48, 28
4. (a) JACS, 2002, 124, 13597; (b) Organometallics, 2003, 22, 1047; (c) Organometallics, 2003, 22, 4451.
5. Organometallics, 2011, 30, 6166.

Publications

Journal articles

  • Ivko SA, Bailey T, Brammer L & Haynes A (2022) . Chemical Communications.
  • Ivko SA, James AM, Derry MJ, Dawson R & Haynes A (2022) . Catalysis Science and Technology, 12(2), 664-673.
  • Aoki Y, Bauer M, Braun T, Cadge JA, Clarke GE, Durand DJ, Eisenstein O, Gallarati S, Greaves M, Harvey J , Haynes A et al (2019) . Faraday Discussions, 220, 282-316.
  • Aoki Y, Bauer M, Braun T, Cadge J, Davies D, Durand DJ, Eisenstein O, Ess D, Fairlamb I, Fey N , Gallarati S et al (2019) . Faraday Discussions, 220, 144-178.
  • Grigoropoulos A, Mckay AI, Katsoulidis AP, Davies RP, Haynes A, Brammer L, Xiao J, Weller AS & Rosseinsky MJ (2018) . Angewandte Chemie International Edition, 57(17), 4532-4537.
  • Grigoropoulos A, McKay AI, Katsoulidis AP, Davies RP, Haynes A, Brammer L, Xiao J, Weller AS & Rosseinsky MJ (2018) . Angewandte Chemie, 130(17), 4622-4627.
  • Repper SE, Haynes A, Ditzel EJ & Sunley GJ (2017) . Dalton Transactions, 46(9), 2821-2828.
  • Grigoropoulos A, Whitehead GFS, Perret N, Katsoulidis AP, Chadwick FM, Davies RP, Haynes A, Brammer L, Weller AS, Xiao J & Rosseinsky MJ (2016) . Chemical Science, 7(3), 2037-2050.
  • Haynes A, Elliott PIP, Haak S, Meijer AJHM & Sunley GJ (2013) . Dalton Transactions, 42(47), 16538-16546.
  • Birbeck JM, Haynes A, Adams H, Damoense L & Otto S (2012) . ACS Catalysis, 2(12), 2512-2523.
  • Williams GL, Parks CM, Smith CR, Adams H, Haynes A, Meijer AJHM, Sunley GJ & Gaemers S (2011) . Organometallics, 30(22), 6166-6179.
  • Conifer CM, Law DJ, Sunley GJ, Haynes A, Wells JR, White AJP & Britovsek GJP (2011) . European Journal of Inorganic Chemistry(23), 3511-3522.
  • Lorenzini F, O'Hara E, Qian SM, Marchetti F, Birbeck JM, Haynes A, Blake AJ, Saunders GC & Marr AC (2009) . Inorganic Chemistry Communications, 12(10), 1071-1073.
  • Haynes A, Meijer AJHM, Lyons JR & Adams H (2009) . Inorg Chem, 48(1), 28-35.
  • Best J, Wilson JM, Adams H, Gonsalvi L, Peruzzini M & Haynes A (2007) . Organometallics, 26(8), 1960-1965.
  • Baber RA, Haddow MF, Middleton AJ, Orpen AG, Pringle PG, Haynes A, Williams GL & Papp R (2007) . Organometallics, 26(3), 713-725.
  • Elliott PIP, Haslam CE, Spey SE & Haynes A (2006) . Inorg Chem, 45(16), 6269-6275.
  • McConnell AC, Pogorzelec PJ, Slawin AMZ, Williams GL, Elliott PIP, Haynes A, Marr AC & Cole-Hamilton DJ (2006) . Dalton Transactions(1), 91-107.
  • Wilson JM, Sunley GJ, Adams H & Haynes A (2005) . Journal of Organometallic Chemistry, 690(24-25), 6089-6095.
  • Maitlis PM, Haynes A, James BR, Catellani M & Chiusoli GP (2004) . Dalton Trans(21), 3409-3419.
  • Haynes A, Haslam CE, Bonnington KJ, Parish L, Adams H, Spey SE, Marder TB & Coventry DN (2004) . Organometallics, 23(25), 5907-5909.
  • Vickers PW, Pearson JM, Ghaffar T, Adams H & Haynes A (2004) . Journal of Physical Organic Chemistry, 17(11), 1007-1016.
  • Haynes A, Maitlis PM, Stanbridge IA, Haak S, Pearson JM, Adams H & Bailey NA (2004) . Inorganica Chimica Acta, 357(10), 3027-3037.
  • Gaunt JA, Gibson VC, Haynes A, Spitzmesser SK, White AJP & Williams DJ (2004) . Organometallics, 23(5), 1015-1023.
  • Haynes A, Maitlis PM, Morris GE, Sunley GJ, Adams H, Badger PW, Bowers CM, Cook DB, Elliott PIP, Ghaffar T , Green H et al (2004) . J Am Chem Soc, 126(9), 2847-2861.
  • Martin HC, James NH, Aitken J, Gaunt JA, Adams H & Haynes A (2003) . Organometallics, 22(22), 4451-4458.
  • Wilkin OM, Maitlis PM, Haynes A & Turner ML (2003) . Catalysis Today, 81(3), 309-317.
  • Gonsalvi L, Gaunt JA, Adams H, Castro A, Sunley GJ & Haynes A (2003) . Organometallics, 22(5), 1047-1054.
  • Gonsalvi L, Adams H, Sunley GJ, Ditzel E & Haynes A (2002) . J Am Chem Soc, 124(45), 13597-13612.
  • Chauby V, Daran JC, Serra-Le Berre C, Malbosc F, Kalck P, Gonzalez OD, Haslam CE & Haynes A (2002) . Inorganic Chemistry, 41(12), 3280-3290.
  • Haynes A, Maitlis PM, Quyoum R, Pulling C, Adams H, Spey SE & Strange RW (2002) . J Chem Soc, Dalton Transactions(12), 2565-2572.
  • Tilset M, Fjeldahl I, Hamon JR, Hamon P, Toupet L, Saillard JY, Costuas K & Haynes A (2001) . J Am Chem Soc, 123(41), 9984-10000.
  • Haynes A (2001) Two Metals are Better Than One. Education in Chemistry, 38(4), 99.
  • Ghaffar T, Charmant JPH, Sunley GJ, Morris GE, Haynes A & Maitlis PM (2000) . Inorganic Chemistry Communications, 3(1), 11-12.
  • Gonsalvi L, Adams H, Sunley GJ, Ditzel E & Haynes A (1999) . J Am Chem Soc, 121(48), 11233-11234.
  • Yang J, Haynes A & Maitlis PM (1999) . Chemical Communications(2), 179-180.
  • Ghaffar T, Adams H, Maitlis PM, Sunley GJ, Baker MJ & Haynes A (1998) . Chemical Communications(9), 1023-1024.
  • Haynes A, Pearson JM, Vickers PW, Charmant JPH & Maitlis PM (1998) . Inorganica Chimica Acta, 270(1-2), 382-391.
  • Haynes A, McNish J & Pearson JM (1998) . J Organomet Chem, 551(1-2), 339-347.
  • Muir JE, Haynes A & Winter MJ (1996) . Chemical Communications(15), 1765-1766.
  • Maitlis PM, Haynes A, Sunley GJ & Howard MJ (1996) . J Chem Soc Dalton Transactions(11), 2187-2196.
  • Griffin TR, Cook DB, Haynes A, Pearson JM, Monti D & Morris GE (1996) . J Am Chem Soc, 118(12), 3029-3030.
  • Monti D, Frachey G, Bassetti M, Haynes A, Sunley GJ, Maitlis PM, Cantoni A & Bocelli G (1995) . Inorganica Chimica Acta, 240(1-2), 485-493.
  • Pearson JM, Haynes A, Morris GE, Sunley GJ & Maitlis PM (1995) . J Chem Soc Chemical Communications(10), 1045-1046.
  • Ellis PR, Pearson JM, Haynes A, Adams H, Bailey NA & Maitlis PM (1994) . Organometallics, 13(8), 3215-3226.
  • Haynes A, Mann BE, Morris GE & Maitlis PM (1993) . J Am Chem Soc, 115(10), 4093-4100.
  • Bassetti M, Monti D, Haynes A, Pearson JM, Stanbridge IA & Maitlis PM (1992) Relative Reaction Rates for Rhodium and Iridium: Oxidative Addition of Methyl Iodide to M(I) and Migratory Insertion in M(III) Methyl Carbonyl Complexes. Gazzetta Chimica Italiana, 122(9), 391-393.
  • Haynes A, Ellis P, Byers P & Maitlis P (1992) Fe(CO)5 in CO cylinders. Chemistry in Britain, 28(6), 517-517.
  • Haynes A, Mann BE, Gulliver DJ, Morris GE & Maitlis PM (1991) . J Am Chem Soc, 113(22), 8567-8569.
  • Haynes A, George MW, Haward MT, Poliakoff M, Turner JJ, Boag NM & Green M (1991) . J Am Chem Soc, 113(6), 2011-2020.
  • Haynes A, Poliakoff M, Turner JJ, Bender BR & Norton JR (1990) . J Organomet Chem, 383(1-3), 497-519.
  • Haynes A & Legon AC (1988) . J Mol Struct, 189(1-2), 153-164.
  • Dixon AJ, Firth S, Haynes A, Poliakoff M, Turner JJ & Boag NM (1988) . J Chem Soc Dalton Transactions(6), 1501-1507.

Book chapters

  • Haynes A (2021) (pp. 333-362). Wiley
  • Haynes A (2017) , Contemporary Catalysis: Science, Technology, and Applications (pp. 793-822). The Royal Society of Chemistry
  • Haynes A (2013) In Reedijk J & Poeppelmeier K (Ed.), Comprehensive Inorganic Chemistry II: From Elements to Applications (pp. 1-24). Elsevier
  • Haynes A (2010) In Gates BC & Knözinger H (Ed.), Advances in Catalysis (pp. 1-45).
  • Maitlis P & Haynes A (2007) , Metal Catalysis in Industrial Organic Processes (pp. 114-162).
  • Haynes A (2006) In Crabtree RH & Mingos DMP (Ed.), Comprehensive Organometallic Chemistry III (pp. 427-444). Elsevier
  • Haynes A & Maitlis PM (2006) In Chiusoli GP & Maitlis PM (Ed.), Metal-catalysis in industrial organic processes (pp. 114-162). RSC
  • Haynes A (2006) In Beller M (Ed.), Catalytic Carbonylation Reactions (pp. 179-205).
  • Haynes A (2005) In Heaton B (Ed.), Mechanisms in Homogeneous Catalysis: A Spectroscopic Approach (pp. 107-150). Wiley VCH
  • Wilkin OM, Allen RWK, Maitlis PM, Tippetts JR, Turner ML, Tesar V, Haynes A, Pitt MJ, Low YY & Sowerby B (2002) In Derouane EG, Parmon V, Lemos F & Ribeiro FR (Ed.), Principles and Methods for Accelerated Catalyst Design and Testing (pp. 299-303).
  • Haynes A, Maitlis PM, Quyoum R, Adams H & Strange RW (2001) In Sherrington DC & Kybett AP (Ed.), Supported Catalysts and their Applications (pp. 166-175).
  • Haynes A & Davies PR (2000) Chemical Marriage Brokers In Lister T (Ed.), Cutting edge chemistry (pp. 55-76). RSC
  • Haynes A & Davies PR (1999) Chemical Mariage Brokers In Hall N (Ed.), The Age of the Molecule (pp. 73-96). RSC
  • Maitlis PM, Turner ML, Quyoum R, Long HC & Haynes A (1998) , Selective Reactions of Metal-Activated Molecules (pp. 83-93). Springer Berlin Heidelberg

Book reviews

  • Haynes A (2009) . Angewandte Chemie International Edition, 48(33), 5993-5993.

Conference proceedings

  • Cavallo L & Haynes A (2002) Steric and electronic effects in the rhodium-catalyzed carbonylation reactions. Abstr Pap Am Chem Soc, Vol. 224 (pp U734-U734)
  • Graziani M & Rao CNR (1993) . Advances in Catalyst Design (pp 1-411)
  • Norton JR, Bender BR, Wiser D, Haynes A, Poliakoff M & Turner JJ (1989) Os2(CO)8, an apparent intermediate in the olefin and acetylene exchange-reactions of diosmacyclobutanes. Abstr Pap Am Chem Soc, Vol. 198 (pp 329-INOR)

Patents

  • Haynes A, Law DJ, Miller A, Morris GE, Payne MJ & Sunley JG (2005) Catalyst and Process for the Production of Acetic Acid. WO2005009939 Appl. 05 Nov 2025.

Preprints

  • Ivko S, James A, Derry M, Dawson R & Haynes A (2021) , American Chemical Society (ACS).
  • Ivko S, James A, Derry M, Dawson R & Haynes A (2021) , American Chemical Society (ACS).
Teaching interests

Transition Metal Chemistry; Homogeneous Catalysis

Teaching activities

Undergraduate and postgraduate taught modules

  • Hydrogen and the s- and p-block elements (Level 1)
    This segment introduces key concepts regarding the structures and properties of the s- and p-block elements.
  • Reactivity and mechanisms of d-block complexes (Level 2)
    This course describes and explains the reaction mechanisms of transition metal complexes.
  • Organometallic Chemistry 1: longitudinal ligands (Level 3)
    This segment deals with the synthesis, structure, bonding and reactivity of transition metal complexes containing metal-carbon σ-bonds. It introduces the role of these complexes in catalytic reactions.
  • Homogeneous Catalysis (Level 4)
    This course describes the chemical basis behind some economically important industrial processes which use homogeneous transition metal catalysts to manufacture important products such as solvents, pharmaceuticals, polymers and detergents.

Support Teaching:

  • Tutorials: Level 1 General Chemistry.
  • Tutorials: Level 2 Inorganic Chemistry.
  • Skills for Success: Database Project.
  • Level 3 Literature Review

Laboratory Teaching:

  • Level 4 Research Project