Promotion of Iridium-Catalyzed Methanol Carbonylation: Mechanistic Studies of the Cativa Process

Anthony Haynes, Peter M. Maitlis, George E. Morris, Glenn J. Sunley, Harry Adams, Peter W. Badger, Craig M. Bowers, David B. Cook, Paul I P Elliott, Talit Ghaffar, Helena Green, Tim R. Griffin, Marc Payne, Jean M. Pearson, Michael J. Taylor, Paul W. Vickers, Rob J. Watt

Research output: Contribution to journalArticle

170 Citations (Scopus)

Abstract

The iridium/iodide-catalyzed carbonylation of methanol to acetic acid is promoted by carbonyl complexes of W, Re, Ru, and Os and simple iodides of Zn, Cd, Hg, Ga, and In. Iodide salts (LiI and Bu4NI) are catalyst poisons. In situ IR spectroscopy shows that the catalyst resting state (at H2O levels ≥ 5% w/w) is fac, cis-[Ir(CO)2I 3Me]-, 2. The stoichiometric carbonylation of 2 into [Ir(CO)2I3(COMe)]-, 6, is accelerated by substoichiometric amounts of neutral promoter species (e.g., [Ru(CO) 3I2]2, [Ru(CO)2I2] n, InI3, GaI3, and ZnI2). The rate increase is approximately proportional to promoter concentration for promoter: Ir ratios of 0-0.2. By contrast anionic Ru complexes (e.g., [Ru(CO) 3I3]-, [Ru(CO)3I3] -, [Ru(CO)2I4]2-) do not promote carbonylation of 2 and Bu4NI is an inhibitor. Mechanistic studies indicate that the promoters accelerate carbonylation of 2 by abstracting an iodide ligand from the Ir center, allowing coordination of CO to give [Ir(CO)3I2Me], 4, identified by high-pressure IR and NMR spectroscopy. Migratory CO insertion is ca. 700 times faster for 4 than for 2 (85 °C, PhCl), representing a lowering of ΔG‡ by 20 kJ mol -1. Ab initio calculations support a more facile methyl migration in 4, the principal factor being decreased π-back-donation to the carbonyl ligands compared to 2. The fac, cis isomer of [Ir(CO)2I 3(COMe)]-, 6a (as its Ph4As+ salt), was characterized by X-ray crystallography. A catalytic mechanism is proposed in which the promoter [M(CO)mIn] (M = Ru, In; m = 3, 0; n = 2, 3) binds I- to form [M(CO)mIn+1] -H3O+ and catalyzes the reaction HI (aq) + MeOAc → Mel + HOAc. This moderates the concentration of HI(aq) and so facilitates catalytic turnover via neutral 4.

LanguageEnglish
Pages2847-2861
Number of pages15
JournalJournal of the American Chemical Society
Volume126
Issue number9
Early online date17 Feb 2004
DOIs
Publication statusPublished - 10 Mar 2004
Externally publishedYes

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Carbonylation
Iridium
Carbon Monoxide
Methanol
Infrared spectroscopy
Ligands
Iodides
Salts
Catalysts
X ray crystallography
Acetic acid
Isomers
Nuclear magnetic resonance spectroscopy
Poisons
X Ray Crystallography
Acetic Acid
Spectrum Analysis
Magnetic Resonance Spectroscopy

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Haynes, A., Maitlis, P. M., Morris, G. E., Sunley, G. J., Adams, H., Badger, P. W., ... Watt, R. J. (2004). Promotion of Iridium-Catalyzed Methanol Carbonylation: Mechanistic Studies of the Cativa Process. Journal of the American Chemical Society, 126(9), 2847-2861. https://doi.org/10.1021/ja039464y
Haynes, Anthony ; Maitlis, Peter M. ; Morris, George E. ; Sunley, Glenn J. ; Adams, Harry ; Badger, Peter W. ; Bowers, Craig M. ; Cook, David B. ; Elliott, Paul I P ; Ghaffar, Talit ; Green, Helena ; Griffin, Tim R. ; Payne, Marc ; Pearson, Jean M. ; Taylor, Michael J. ; Vickers, Paul W. ; Watt, Rob J. / Promotion of Iridium-Catalyzed Methanol Carbonylation : Mechanistic Studies of the Cativa Process. In: Journal of the American Chemical Society. 2004 ; Vol. 126, No. 9. pp. 2847-2861.
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abstract = "The iridium/iodide-catalyzed carbonylation of methanol to acetic acid is promoted by carbonyl complexes of W, Re, Ru, and Os and simple iodides of Zn, Cd, Hg, Ga, and In. Iodide salts (LiI and Bu4NI) are catalyst poisons. In situ IR spectroscopy shows that the catalyst resting state (at H2O levels ≥ 5{\%} w/w) is fac, cis-[Ir(CO)2I 3Me]-, 2. The stoichiometric carbonylation of 2 into [Ir(CO)2I3(COMe)]-, 6, is accelerated by substoichiometric amounts of neutral promoter species (e.g., [Ru(CO) 3I2]2, [Ru(CO)2I2] n, InI3, GaI3, and ZnI2). The rate increase is approximately proportional to promoter concentration for promoter: Ir ratios of 0-0.2. By contrast anionic Ru complexes (e.g., [Ru(CO) 3I3]-, [Ru(CO)3I3] -, [Ru(CO)2I4]2-) do not promote carbonylation of 2 and Bu4NI is an inhibitor. Mechanistic studies indicate that the promoters accelerate carbonylation of 2 by abstracting an iodide ligand from the Ir center, allowing coordination of CO to give [Ir(CO)3I2Me], 4, identified by high-pressure IR and NMR spectroscopy. Migratory CO insertion is ca. 700 times faster for 4 than for 2 (85 °C, PhCl), representing a lowering of ΔG‡ by 20 kJ mol -1. Ab initio calculations support a more facile methyl migration in 4, the principal factor being decreased π-back-donation to the carbonyl ligands compared to 2. The fac, cis isomer of [Ir(CO)2I 3(COMe)]-, 6a (as its Ph4As+ salt), was characterized by X-ray crystallography. A catalytic mechanism is proposed in which the promoter [M(CO)mIn] (M = Ru, In; m = 3, 0; n = 2, 3) binds I- to form [M(CO)mIn+1] -H3O+ and catalyzes the reaction HI (aq) + MeOAc → Mel + HOAc. This moderates the concentration of HI(aq) and so facilitates catalytic turnover via neutral 4.",
author = "Anthony Haynes and Maitlis, {Peter M.} and Morris, {George E.} and Sunley, {Glenn J.} and Harry Adams and Badger, {Peter W.} and Bowers, {Craig M.} and Cook, {David B.} and Elliott, {Paul I P} and Talit Ghaffar and Helena Green and Griffin, {Tim R.} and Marc Payne and Pearson, {Jean M.} and Taylor, {Michael J.} and Vickers, {Paul W.} and Watt, {Rob J.}",
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Haynes, A, Maitlis, PM, Morris, GE, Sunley, GJ, Adams, H, Badger, PW, Bowers, CM, Cook, DB, Elliott, PIP, Ghaffar, T, Green, H, Griffin, TR, Payne, M, Pearson, JM, Taylor, MJ, Vickers, PW & Watt, RJ 2004, 'Promotion of Iridium-Catalyzed Methanol Carbonylation: Mechanistic Studies of the Cativa Process', Journal of the American Chemical Society, vol. 126, no. 9, pp. 2847-2861. https://doi.org/10.1021/ja039464y

Promotion of Iridium-Catalyzed Methanol Carbonylation : Mechanistic Studies of the Cativa Process. / Haynes, Anthony; Maitlis, Peter M.; Morris, George E.; Sunley, Glenn J.; Adams, Harry; Badger, Peter W.; Bowers, Craig M.; Cook, David B.; Elliott, Paul I P; Ghaffar, Talit; Green, Helena; Griffin, Tim R.; Payne, Marc; Pearson, Jean M.; Taylor, Michael J.; Vickers, Paul W.; Watt, Rob J.

In: Journal of the American Chemical Society, Vol. 126, No. 9, 10.03.2004, p. 2847-2861.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Promotion of Iridium-Catalyzed Methanol Carbonylation

T2 - Journal of the American Chemical Society

AU - Haynes, Anthony

AU - Maitlis, Peter M.

AU - Morris, George E.

AU - Sunley, Glenn J.

AU - Adams, Harry

AU - Badger, Peter W.

AU - Bowers, Craig M.

AU - Cook, David B.

AU - Elliott, Paul I P

AU - Ghaffar, Talit

AU - Green, Helena

AU - Griffin, Tim R.

AU - Payne, Marc

AU - Pearson, Jean M.

AU - Taylor, Michael J.

AU - Vickers, Paul W.

AU - Watt, Rob J.

PY - 2004/3/10

Y1 - 2004/3/10

N2 - The iridium/iodide-catalyzed carbonylation of methanol to acetic acid is promoted by carbonyl complexes of W, Re, Ru, and Os and simple iodides of Zn, Cd, Hg, Ga, and In. Iodide salts (LiI and Bu4NI) are catalyst poisons. In situ IR spectroscopy shows that the catalyst resting state (at H2O levels ≥ 5% w/w) is fac, cis-[Ir(CO)2I 3Me]-, 2. The stoichiometric carbonylation of 2 into [Ir(CO)2I3(COMe)]-, 6, is accelerated by substoichiometric amounts of neutral promoter species (e.g., [Ru(CO) 3I2]2, [Ru(CO)2I2] n, InI3, GaI3, and ZnI2). The rate increase is approximately proportional to promoter concentration for promoter: Ir ratios of 0-0.2. By contrast anionic Ru complexes (e.g., [Ru(CO) 3I3]-, [Ru(CO)3I3] -, [Ru(CO)2I4]2-) do not promote carbonylation of 2 and Bu4NI is an inhibitor. Mechanistic studies indicate that the promoters accelerate carbonylation of 2 by abstracting an iodide ligand from the Ir center, allowing coordination of CO to give [Ir(CO)3I2Me], 4, identified by high-pressure IR and NMR spectroscopy. Migratory CO insertion is ca. 700 times faster for 4 than for 2 (85 °C, PhCl), representing a lowering of ΔG‡ by 20 kJ mol -1. Ab initio calculations support a more facile methyl migration in 4, the principal factor being decreased π-back-donation to the carbonyl ligands compared to 2. The fac, cis isomer of [Ir(CO)2I 3(COMe)]-, 6a (as its Ph4As+ salt), was characterized by X-ray crystallography. A catalytic mechanism is proposed in which the promoter [M(CO)mIn] (M = Ru, In; m = 3, 0; n = 2, 3) binds I- to form [M(CO)mIn+1] -H3O+ and catalyzes the reaction HI (aq) + MeOAc → Mel + HOAc. This moderates the concentration of HI(aq) and so facilitates catalytic turnover via neutral 4.

AB - The iridium/iodide-catalyzed carbonylation of methanol to acetic acid is promoted by carbonyl complexes of W, Re, Ru, and Os and simple iodides of Zn, Cd, Hg, Ga, and In. Iodide salts (LiI and Bu4NI) are catalyst poisons. In situ IR spectroscopy shows that the catalyst resting state (at H2O levels ≥ 5% w/w) is fac, cis-[Ir(CO)2I 3Me]-, 2. The stoichiometric carbonylation of 2 into [Ir(CO)2I3(COMe)]-, 6, is accelerated by substoichiometric amounts of neutral promoter species (e.g., [Ru(CO) 3I2]2, [Ru(CO)2I2] n, InI3, GaI3, and ZnI2). The rate increase is approximately proportional to promoter concentration for promoter: Ir ratios of 0-0.2. By contrast anionic Ru complexes (e.g., [Ru(CO) 3I3]-, [Ru(CO)3I3] -, [Ru(CO)2I4]2-) do not promote carbonylation of 2 and Bu4NI is an inhibitor. Mechanistic studies indicate that the promoters accelerate carbonylation of 2 by abstracting an iodide ligand from the Ir center, allowing coordination of CO to give [Ir(CO)3I2Me], 4, identified by high-pressure IR and NMR spectroscopy. Migratory CO insertion is ca. 700 times faster for 4 than for 2 (85 °C, PhCl), representing a lowering of ΔG‡ by 20 kJ mol -1. Ab initio calculations support a more facile methyl migration in 4, the principal factor being decreased π-back-donation to the carbonyl ligands compared to 2. The fac, cis isomer of [Ir(CO)2I 3(COMe)]-, 6a (as its Ph4As+ salt), was characterized by X-ray crystallography. A catalytic mechanism is proposed in which the promoter [M(CO)mIn] (M = Ru, In; m = 3, 0; n = 2, 3) binds I- to form [M(CO)mIn+1] -H3O+ and catalyzes the reaction HI (aq) + MeOAc → Mel + HOAc. This moderates the concentration of HI(aq) and so facilitates catalytic turnover via neutral 4.

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