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Title: In situ high pressure NMR studies of Co{sub 2}(CO){sub 6}[P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 3}]{sub 2} in supercritical carbon dioxide : ligand substitution, hydrogenation, and hydroformylation reactions.

Abstract

The dimeric cobalt complex Co{sub 2}(CO){sub 6}[P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 3}]{sub 2} (1) reacts reversibly with hydrogen to produce HCo(CO){sub 3}[P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 3}] (4). The carbonyl and the phosphine ligands of both 1 and 4 are very labile. Compound 1 reacts with CO to give Co{sub 2}(CO){sub 7}[P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 3}] (2), and compound 4 reacts with CO and P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 3} (L) to give HCo(CO){sub 4} (5) and HCo(CO){sub 2}[P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 3}]{sub 2} (6), respectively. The {sup 31}P NMR studies show that, in the presence of 1, the line width of the {sup 31}P resonance of L is temperature dependent, and at constant temperature, its broadening is proportional to the square root of the concentration of 1. This broadening is attributed to its exchange reaction with the mononuclear cobalt radical (CO){sub 3}LCo{sup {sm_bullet}} (3), which is generated by the homolysis of 1. Compound 1 catalyzes the hydroformylation of olefins in supercritical carbon dioxide. In contrast to the unsubstituted Co{sub 2}(CO){sub 8}, the phosphine-modified catalyst system is stable under low CO pressures and the hydroformylation reactions can be carried out at low pressures. In situ monitoring of {sup 31}P and {sup 59}Co NMRmore » spectra of the solution shows that the phosphine-containing hydrido cobalt complexes 4 and 6 are the only hydrido cobalt complexes present in detectable concentrations in 1-catalyzed hydroformylation reactions; nevertheless, the possibility that the observed activity for 1 comes primarily from the more active HCo(CO){sub 4}, present in concentrations below detectable limits, has not been rigorously excluded.« less

Authors:
; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
961431
Report Number(s):
ANL/CMT/JA-47705
Journal ID: ISSN 0276-7333; ORGND7; TRN: US201012%%1494
DOE Contract Number:  
DE-AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 23; Journal Issue: 11 ; May 24, 2004; Journal ID: ISSN 0276-7333
Country of Publication:
United States
Language:
ENGLISH
Subject:
08 HYDROGEN; ALKENES; CARBON DIOXIDE; CARBONYLATION; CARBONYLS; CATALYSTS; COBALT; COBALT COMPLEXES; HYDROGEN; HYDROGENATION; LIGANDS; LINE WIDTHS; NMR SPECTRA; NUCLEAR MAGNETIC RESONANCE; PHOSPHINES; PRESSURE RANGE MEGA PA 10-100; RADICALS; RESONANCE; TEMPERATURE DEPENDENCE

Citation Formats

Chen, M J, Klingler, R J, Rathke, J W, Kramarz, K W, Chemical Engineering, and Sunoco Chemicals. In situ high pressure NMR studies of Co{sub 2}(CO){sub 6}[P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 3}]{sub 2} in supercritical carbon dioxide : ligand substitution, hydrogenation, and hydroformylation reactions.. United States: N. p., 2004. Web. doi:10.1021/om030600h.
Chen, M J, Klingler, R J, Rathke, J W, Kramarz, K W, Chemical Engineering, & Sunoco Chemicals. In situ high pressure NMR studies of Co{sub 2}(CO){sub 6}[P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 3}]{sub 2} in supercritical carbon dioxide : ligand substitution, hydrogenation, and hydroformylation reactions.. United States. https://doi.org/10.1021/om030600h
Chen, M J, Klingler, R J, Rathke, J W, Kramarz, K W, Chemical Engineering, and Sunoco Chemicals. Mon . "In situ high pressure NMR studies of Co{sub 2}(CO){sub 6}[P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 3}]{sub 2} in supercritical carbon dioxide : ligand substitution, hydrogenation, and hydroformylation reactions.". United States. https://doi.org/10.1021/om030600h.
@article{osti_961431,
title = {In situ high pressure NMR studies of Co{sub 2}(CO){sub 6}[P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 3}]{sub 2} in supercritical carbon dioxide : ligand substitution, hydrogenation, and hydroformylation reactions.},
author = {Chen, M J and Klingler, R J and Rathke, J W and Kramarz, K W and Chemical Engineering and Sunoco Chemicals},
abstractNote = {The dimeric cobalt complex Co{sub 2}(CO){sub 6}[P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 3}]{sub 2} (1) reacts reversibly with hydrogen to produce HCo(CO){sub 3}[P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 3}] (4). The carbonyl and the phosphine ligands of both 1 and 4 are very labile. Compound 1 reacts with CO to give Co{sub 2}(CO){sub 7}[P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 3}] (2), and compound 4 reacts with CO and P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 3} (L) to give HCo(CO){sub 4} (5) and HCo(CO){sub 2}[P(p-CF{sub 3}C{sub 6}H{sub 4}){sub 3}]{sub 2} (6), respectively. The {sup 31}P NMR studies show that, in the presence of 1, the line width of the {sup 31}P resonance of L is temperature dependent, and at constant temperature, its broadening is proportional to the square root of the concentration of 1. This broadening is attributed to its exchange reaction with the mononuclear cobalt radical (CO){sub 3}LCo{sup {sm_bullet}} (3), which is generated by the homolysis of 1. Compound 1 catalyzes the hydroformylation of olefins in supercritical carbon dioxide. In contrast to the unsubstituted Co{sub 2}(CO){sub 8}, the phosphine-modified catalyst system is stable under low CO pressures and the hydroformylation reactions can be carried out at low pressures. In situ monitoring of {sup 31}P and {sup 59}Co NMR spectra of the solution shows that the phosphine-containing hydrido cobalt complexes 4 and 6 are the only hydrido cobalt complexes present in detectable concentrations in 1-catalyzed hydroformylation reactions; nevertheless, the possibility that the observed activity for 1 comes primarily from the more active HCo(CO){sub 4}, present in concentrations below detectable limits, has not been rigorously excluded.},
doi = {10.1021/om030600h},
url = {https://www.osti.gov/biblio/961431}, journal = {Organometallics},
issn = {0276-7333},
number = 11 ; May 24, 2004,
volume = 23,
place = {United States},
year = {2004},
month = {5}
}