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

Journal of the American Chemical Society

Volumn 126, Issue 9, 2004, Pages 2847-2861

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

^a UNIVERSITY OF SHEFFIELD   (United Kingdom)

^b BP EXPLORATION   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

CARBONYLATION; CATALYSIS; COMPLEXATION; INFRARED SPECTROSCOPY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION KINETICS; STOICHIOMETRY; X RAY CRYSTALLOGRAPHY;

CARBONYL COMPLEXES; NEUTRAL PROMOTER SPECIES;

IRIDIUM COMPOUNDS;

ACETIC ACID; ARSENIC DERIVATIVE; CADMIUM DERIVATIVE; CARBON MONOXIDE; CARBONYL DERIVATIVE; COORDINATION COMPOUND; GALLIUM; INDIUM; IODIDE; LIGAND; LITHIUM DERIVATIVE; MERCURY DERIVATIVE; METHANOL; METHYL GROUP; OSMIUM DERIVATIVE; PALLADIUM; RHENIUM COMPLEX; RUTHENIUM COMPLEX; TUNGSTEN DERIVATIVE; WATER; ZINC DERIVATIVE;

AB INITIO CALCULATION; ARTICLE; CARBONYLATION; CATALYSIS; CATALYST; CHEMICAL BINDING; CHEMICAL REACTION; CHEMICAL REACTION KINETICS; CIS ISOMER; CONCENTRATION (PARAMETERS); ENERGY; INFRARED SPECTROSCOPY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; REACTION ANALYSIS; STOICHIOMETRY; X RAY CRYSTALLOGRAPHY;

EID: 84962345984     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja039464y     Document Type: Article

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85. n- (x = 2 or 3, y = 3 or 2, n = 1 or 0).
86. In support of this, Mulliken population analysis indicates that the partial charge on the carbon of a CO cis to methyl decreases from +0.32 in 4 to +0.26 in 2. Also the appropriate unoccupied acceptor orbital (an out of phase combination of π*CO with dπ) is significantly higher in energy for than for 4 (0.160 and 0.039 hartrees respectively).
87. 1H NMR spectroscopy: an MeCN solution containing equimolar 6a and 3-NCMe attained an equilibrium in which ca. 50% of 3-NCMe was converted into 2.
88. -: Suss-Fink, G.; Haak, S.; Ferrand, V.; Stoeckli-Evans, H. J. Mol. Catal. A-Chem. 1999, 143, 163.
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91. Arndt, L. W.; Bancroft, B. T.; Darensbourg, M. Y.; Janzeri, C. P.; Kim, C. M.; Reibenspies, J.; Varner, K. E.; Youngdahl, K. A. Organometallics 1988, 7, 1302.
92. 3 to the cooled catalytic reaction mixture. However, ref 33 shows that P-donor ligands can induce CO insertion in 2 to give products of this type, so isolation of an Ir-acetyl does not show it to be the catalytic resting state. Methanolysis of 6 to give MeOAc is slow at ambient temperature but observable at ca. 50 °C. The much higher temperature and presence of water make it likely that solvolysis of 6 is relatively fast under process conditions. A pre-equilibrium 2 + CO = 6 followed by rate-determining solvolysis of 6 would result in a first-order dependence on [CO], which is not observed. Although 6 reverts to 2 + CO on heating in the absence of added CO, the equilibrium favors 6 even at 5 bar CO. Therefore if solvolysis of 6 were rate-determining, one would expect to observe it (rather than 2) as the resting state at higher pCO.
93. Fulford, A.; Hickey, C. E.; Maitlis, P. M. J. Organomet. Chem. 1990, 398, 311. Ivanova, E. A.; Gisdakis, P.; Nasluzov, V. A.; Rubailo, A. I.; Rösch, N. Organometallics 2001, 20, 1161. Griffin, T. R.; Cook, D. B.; Haynes, A.; Pearson, J. M.; Monti, D.; Morris, G. E. J. Am. Chem. Soc. 1996, 118, 3029. Rendina, L. M.; Puddephatt, R. J. Chem. Rev. 1997, 97, 1735. Labinger, J. A.; Osborn, J. A. Inorg. Chem. 1980, 19, 3230.
94. Fulford, A.; Hickey, C. E.; Maitlis, P. M. J. Organomet. Chem. 1990, 398, 311. Ivanova, E. A.; Gisdakis, P.; Nasluzov, V. A.; Rubailo, A. I.; Rösch, N. Organometallics 2001, 20, 1161. Griffin, T. R.; Cook, D. B.; Haynes, A.; Pearson, J. M.; Monti, D.; Morris, G. E. J. Am. Chem. Soc. 1996, 118, 3029. Rendina, L. M.; Puddephatt, R. J. Chem. Rev. 1997, 97, 1735. Labinger, J. A.; Osborn, J. A. Inorg. Chem. 1980, 19, 3230.
95. Fulford, A.; Hickey, C. E.; Maitlis, P. M. J. Organomet. Chem. 1990, 398, 311. Ivanova, E. A.; Gisdakis, P.; Nasluzov, V. A.; Rubailo, A. I.; Rösch, N. Organometallics 2001, 20, 1161. Griffin, T. R.; Cook, D. B.; Haynes, A.; Pearson, J. M.; Monti, D.; Morris, G. E. J. Am. Chem. Soc. 1996, 118, 3029. Rendina, L. M.; Puddephatt, R. J. Chem. Rev. 1997, 97, 1735. Labinger, J. A.; Osborn, J. A. Inorg. Chem. 1980, 19, 3230.
96. Fulford, A.; Hickey, C. E.; Maitlis, P. M. J. Organomet. Chem. 1990, 398, 311. Ivanova, E. A.; Gisdakis, P.; Nasluzov, V. A.; Rubailo, A. I.; Rösch, N. Organometallics 2001, 20, 1161. Griffin, T. R.; Cook, D. B.; Haynes, A.; Pearson, J. M.; Monti, D.; Morris, G. E. J. Am. Chem. Soc. 1996, 118, 3029. Rendina, L. M.; Puddephatt, R. J. Chem. Rev. 1997, 97, 1735. Labinger, J. A.; Osborn, J. A. Inorg. Chem. 1980, 19, 3230.
97. Fulford, A.; Hickey, C. E.; Maitlis, P. M. J. Organomet. Chem. 1990, 398, 311. Ivanova, E. A.; Gisdakis, P.; Nasluzov, V. A.; Rubailo, A. I.; Rösch, N. Organometallics 2001, 20, 1161. Griffin, T. R.; Cook, D. B.; Haynes, A.; Pearson, J. M.; Monti, D.; Morris, G. E. J. Am. Chem. Soc. 1996, 118, 3029. Rendina, L. M.; Puddephatt, R. J. Chem. Rev. 1997, 97, 1735. Labinger, J. A.; Osborn, J. A. Inorg. Chem. 1980, 19, 3230.
98. The estimated contribution of methyl migration in 2 to the catalytic activity is based on the rate measured at 15:1 LiI:Ir, which is ca. 10% of the rate in the absence of LiI. Since the in situ HPIR shows the Ir speciation to be >90% and ca. 50% 2, respectively, with or without LiI, methyl migration in 2 can account for ≤5% of the catalytic rate in the absence of LiI.
99. - have recently been undertaken by Merbach and co-workers: Churland, R.; Frey, U.; Metz, F.; Merbach, A. E. Inorg. Chem. 2000, 39, 304; 2000, 39, 4137.
100. - have recently been undertaken by Merbach and co-workers: Churland, R.; Frey, U.; Metz, F.; Merbach, A. E. Inorg. Chem. 2000, 39, 304; 2000, 39, 4137.
101. -1) (25 °C, MeCN).
102. - in the catalytic medium (aqueous acetic acid).
103. +" can activate methyl acetate by protonation: Braca, G.; Sbrana, G.; Valentini, G.; Andrich, G.; Gregorio, G. J. Am. Chem. Soc. 1978, 100, 6238.
104. +.
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