Haynes, Anthony - University of Sheffield

个人简介

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).

研究领域

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 Rh-xant-TSWe 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]

近期论文

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Grigoropoulos A, Whitehead GFS, Perret N, Katsoulidis AP, Chadwick FM, Davies RP, Haynes A, Brammer L, Weller AS, Xiao J & Rosseinsky MJ (2016) Encapsulation of an organometallic cationic catalyst by direct exchange into an anionic MOF. Chem. Sci., 7(3), 2037-2050. View this article in WRRO Haynes A, Elliott PIP, Haak S, Meijer AJHM & Sunley GJ (2013) Reactivity of Ir(III) carbonyl complexes with water: alternative by-product formation pathways in catalytic methanol carbonylation. Dalton Transactions, 42(47), 16538-16546. View this article in WRRO Birbeck JM, Haynes A, Adams H, Damoense L & Otto S (2012) Ligand effects on reactivity of cobalt acyl complexes. ACS Catalysis, 2(12), 2512-2523. Williams GL, Parks CM, Smith CR, Adams H, Haynes A, Meijer AJHM, Sunley GJ & Gaemers S (2011) Mechanistic study of rhodium/xantphos-catalyzed methanol carbonylation. Organometallics, 30(22), 6166-6179. Conifer CM, Law DJ, Sunley GJ, Haynes A, Wells JR, White AJP & Britovsek GJP (2011) Dicarbonylrhodium(I) complexes of bipyridine ligands with proximate H-bonding substituents and their application in methyl acetate carbonylation. 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) The structural characterization and hydroformylation activity of the tri-rhodium complex [Rh3(μ2-dppm)2(μ2-CO)3(κ1-CO)3]BF4. Inorganic Chemistry Communications, 12(10), 1071-1073.