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Title: Effect of phosphines on the thermodynamics of the cobalt catalyzed hydroformylation system.

Abstract

Thermodynamic parameters relevant to the phosphine-modified cobalt hydroformylation reaction are reported. Equilibrium constants for the hydrogenation of Co{sub 2}(CO){sub 6}L{sub 2} to yield HCo(CO){sub 3}L were determined using in situ {sup 1}H and {sup 31}P NMR spectroscopy between 75 and 175 C for various solvents and phosphine ligands. Special emphasis was placed on n-Bu{sub 3}P, as this ligand is prototypical of the Shell hydroformylation process. The resultant van't Hoff plots yield the enthalpy and entropy change (H = 7.0 {+-} 0.4 kcal/mol and {Delta}S = 2 {+-} 1 cal/mol {center_dot} K) for the case of L = n-Bu{sub 3}P in benzene solvent. These parameters were found to be relatively insensitive to changes in the solvent, suggesting that the hydride product is not very polar. Even for isobutyl alcohol solvent, the resultant enthalpy and entropy changes (H = 5.8 {+-} 0.4 kcal/mol and S = -2 {+-} 1 cal/mol {center_dot} K) were found to be similar to those obtained in benzene and dioxane. Analysis of the {sup 31}P NMR line widths allows rigorous lower limits to be established for the catalytically relevant Co-Co and Co-H bond energies in the case of L = n-Bu{sub 3}P (Co-Co 23 kcal/mol and Co-H 60more » kcal/mol) relative to the previously reported values for the case of L = CO (Co-Co = 19 {+-} 2 kcal/mol and Co-H = 59 {+-} 1 kcal/mol).« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
935912
Report Number(s):
ANL/CMT/JA-56966
Journal ID: ISSN 0276-7333; ORGND7; TRN: US200816%%1047
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Organometallics; Journal Volume: 26; Journal Issue: 2 ; 2007
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CARBONYLATION; COBALT; CATALYTIC EFFECTS; ENTHALPY; ENTROPY; HYDROGENATION; PHOSPHINES; ORGANIC SOLVENTS; THERMODYNAMICS

Citation Formats

Klingler, R. J., Chen, M. J., Rathke, J. W., Kramarz, K. W., Chemical Engineering, and BASF Corp. Effect of phosphines on the thermodynamics of the cobalt catalyzed hydroformylation system.. United States: N. p., 2007. Web. doi:10.1021/om060768d.
Klingler, R. J., Chen, M. J., Rathke, J. W., Kramarz, K. W., Chemical Engineering, & BASF Corp. Effect of phosphines on the thermodynamics of the cobalt catalyzed hydroformylation system.. United States. doi:10.1021/om060768d.
Klingler, R. J., Chen, M. J., Rathke, J. W., Kramarz, K. W., Chemical Engineering, and BASF Corp. Mon . "Effect of phosphines on the thermodynamics of the cobalt catalyzed hydroformylation system.". United States. doi:10.1021/om060768d.
@article{osti_935912,
title = {Effect of phosphines on the thermodynamics of the cobalt catalyzed hydroformylation system.},
author = {Klingler, R. J. and Chen, M. J. and Rathke, J. W. and Kramarz, K. W. and Chemical Engineering and BASF Corp.},
abstractNote = {Thermodynamic parameters relevant to the phosphine-modified cobalt hydroformylation reaction are reported. Equilibrium constants for the hydrogenation of Co{sub 2}(CO){sub 6}L{sub 2} to yield HCo(CO){sub 3}L were determined using in situ {sup 1}H and {sup 31}P NMR spectroscopy between 75 and 175 C for various solvents and phosphine ligands. Special emphasis was placed on n-Bu{sub 3}P, as this ligand is prototypical of the Shell hydroformylation process. The resultant van't Hoff plots yield the enthalpy and entropy change (H = 7.0 {+-} 0.4 kcal/mol and {Delta}S = 2 {+-} 1 cal/mol {center_dot} K) for the case of L = n-Bu{sub 3}P in benzene solvent. These parameters were found to be relatively insensitive to changes in the solvent, suggesting that the hydride product is not very polar. Even for isobutyl alcohol solvent, the resultant enthalpy and entropy changes (H = 5.8 {+-} 0.4 kcal/mol and S = -2 {+-} 1 cal/mol {center_dot} K) were found to be similar to those obtained in benzene and dioxane. Analysis of the {sup 31}P NMR line widths allows rigorous lower limits to be established for the catalytically relevant Co-Co and Co-H bond energies in the case of L = n-Bu{sub 3}P (Co-Co 23 kcal/mol and Co-H 60 kcal/mol) relative to the previously reported values for the case of L = CO (Co-Co = 19 {+-} 2 kcal/mol and Co-H = 59 {+-} 1 kcal/mol).},
doi = {10.1021/om060768d},
journal = {Organometallics},
number = 2 ; 2007,
volume = 26,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}