Theoretical study of the hydroformylation reaction mechanism

Grima, J.P.; Choplin, F.; Kauffmann, G.

doi:10.1016/s0022-328x(00)92495-1

Cited by 35 publications

(20 citation statements)

References 22 publications

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“…In an early theoretical study on the HCo(CO) 4 -catalyzed hydroformylation of propene, Grima et al proposed that the regioselectivity originates from the electrostatic dipole–dipole interaction between Co–H and CC that favors the anti-Markovnikov insertion . We have analyzed the natural charges on the atoms of the Co–H and CC bonds in IM4 / IM3 and t BuCHCH 2 (Figure ).…”

Section: Resultsmentioning

confidence: 99%

“…Therefore, the electronic factors favor the anti-Markovnikov insertion of t -butylethylene into IM4 over the Markovnikov insertion of t -butylethylene into IM3 . This finding is consistent with the charge effect on the regioselectivity of alkene insertion proposed by Grima et al…”

Section: Resultsmentioning

confidence: 99%

“…The discovery of the cationic Co(II) catalyst system represents a major advance for the field of hydroformylation chemistry, which has inspired our interest. There are a significant number of computational studies on Co(I)-catalyzed alkene hydroformylation. − We wish to study the new cationic Co(II) catalyst system by means of extensive DFT computations. We seek to elucidate the detailed mechanism of the reaction shown in Scheme and gain deep insights into the greater activity of this cationic Co(II) catalyst system in comparison with the neutral Co(I) system.…”

Section: Introductionmentioning

confidence: 99%

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Mechanistic Insights into Hydroformylation Catalyzed by Cationic Cobalt(II) Complexes: In Silico Modification of the Catalyst System

2020

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The hydroformylation reaction is used on a large industrial scale to convert olefins and synthesis gas (CO + H 2 ) into aldehydes. Researchers have recently discovered that a class of cationic Co(II) complexes of the formula [Co II (PP)(acac)] + (PP = diphosphine, acac = acetylacetonate) can catalyze hydroformylation with activity approaching that of the widely used rhodium catalysts (Hood, D. M. et al. Science 2020, 367, 542−548). This density functional theory (DFT) study reveals the detailed workings of the cationic Co(II) catalyst system. The precatalyst [Co II (PP)(acac)] + is initiated by reacting with H 2 and CO to generate active species [HCo II (CO) 2 (PP)] + . In comparison with the 18-electron neutral Co(I) catalytic species HCo I (CO) 3 (PR 3 ), these cationic Co(II) species, with their unique 17-electron and square pyramidal structure, invoke a lower-energy pathway through different elementary steps such as associative alkene uptake and heterolytic H 2 cleavage. The regioselectivity for linear aldehyde products is due to a combination of electronic and steric effects that favor the anti-Markovnikov insertion of a terminal alkene into the Co−H bond. DFT calculations predict that addition of PMe 3 would facilitate the precatalyst initiation, thereby decreasing the reaction temperature or shortening the induction period. The insights gained by this theoretical study can be useful for the further development of hydroformylation catalysts.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Mechanistic Insights into Hydroformylation Catalyzed by Cationic Cobalt(II) Complexes: In Silico Modification of the Catalyst System

2020

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“…Due to its industrial importance, hydroformylation has received considerable attention both experimentally 14-31 and theoretically. − A two-phase system or supercritical carbon dioxide − as reaction medium has improved the product separation situation. Even so, the main research activities in this field are focused on ligand-modified catalysts for obtaining high regioselectivity. ,, Therefore, understanding the mechanism in detail and unraveling the origin of regioselectivity are very crucial.…”

Section: Introductionmentioning

confidence: 99%

HCo(CO)₃-Catalyzed Propene Hydroformylation. Insight into Detailed Mechanism

Huo

Beller

et al. 2003

Organometallics

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The entire catalytic cycle of propene hydroformylation using HCo(CO) 3 as an active catalyst has been systematically investigated at the B3LYP density functional level of theory. It is found that the most stable π-complex HCo(CO) 3 (η 2 -H 2 CdCHCH 3 ) has a CdC double bond coordination in the equatorial position, and the subsequent olefin insertion (alkylation) process is reversible, in agreement with the experimental finding. The hydride migratory insertion is accompanied by Co(CO) 3 pseudorotation, leading to the Co‚‚‚H-C agostic stabilized (iso)propyl complex (C 3 H 7 )Co(CO) 3 with the alkyl group at the axial position and thus does not take place on a C s symmetry potential energy surface. The regioselectivity is mainly determined by the relative stability of the alkyl cobalt tetracarbonyl complexes (C 3 H 7 )-Co(CO) 4 from the exothermic and irreversible CO addition to the alkyl cobalt tricarbonyl complexes (C 3 H 7 )Co(CO) 3 , which is therefore a thermodynamic controlled process. The CO insertion process (carbonylation) proceeds via two Co(CO) 3 pseudorotated transition states and a Co‚‚‚H-C agostic stabilized intermediate. The resulting most stable complex (C 3 H 7 -CO)Co(CO) 3 with the acyl group in the axial site has a η 2 -OdC interaction at the equatorial site, and the computed characteristic vibrational modes agree well with the available experimental data. In contrast to the generally accepted conclusion, H 2 coordination to the acyl complex rather than oxidative addition is the rate-determining step after HCo(CO) 3 generation. This finding is supported by the high stability of the acyl complex toward further H 2 addition, as found experimentally.

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“…Proton- and electron-transfer reactions are the most fundamental reactions in chemistry and biology. Recently, considerable attention was focused on the deprotonation of transition metal hydrides. , Both experimental and theoretical studies show a substantial negative charge on the hydride of HCo(CO) 4 , although HCo(CO) 4 is a strong acid in water and has a p K a in acetonitrile about equal to that of HCl. It has been suggested that the proton transfer proceeds through hydrogen-bonded intermediates .…”

Section: Resultsmentioning

confidence: 99%

The Strong Acidity and the Process for Deprotonation of (η⁶-Toluene)Fe(H)₂(SiCl₃)₂

Yao

Klabunde

1997

Inorg. Chem.

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The acidity and the process for deprotonation of (eta(6)-toluene)Fe(H)(2)(SiCl(3))(2) in acetonitrile were studied with pyridine derivatives. (eta(6)-Toluene)Fe(H)(2)(SiCl(3))(2) is a very strong acid and deprotonates in acetonitrile. The formation of hydrogen-bonded complexes M-H.N prior to deprotonation is observed when pyridine, 2,6-lutidine, and 2,2'-bipyridine are used. With 1 equiv of bipyridine, the hydrogen-bonded species is quite stable, two hydrides are deprotonated, and [bpyH(2)](2+) is formed. The small (57)Fe-hydride coupling constant (3.6 Hz) for (eta(6)-toluene)Fe(H)(2)(SiCl(3))(2) is consistent with strong acidity of the compound. The 10.8 Hz coupling between (57)Fe and the hydride in [(eta(6)-toluene)Fe(H)(SiCl(3))(2)](-) and (eta(6)-toluene)Fe(H)(py)(SiCl(3)) is similar to those observed in other Fe(II) hydrido compounds. The observation of the coupling only between p-H and the hydride in [(eta(6)-toluene)Fe(H)(SiCl(3))(2)](-) and (eta(6)-toluene)Fe(H)(py)(SiCl(3)) indicates that the configuration with the hydride trans to p-H is dominant in solution and the rotation of the toluene is not fast at room temperature.

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Theoretical study of the hydroformylation reaction mechanism

Cited by 35 publications

References 22 publications

Mechanistic Insights into Hydroformylation Catalyzed by Cationic Cobalt(II) Complexes: In Silico Modification of the Catalyst System

Mechanistic Insights into Hydroformylation Catalyzed by Cationic Cobalt(II) Complexes: In Silico Modification of the Catalyst System

HCo(CO)₃-Catalyzed Propene Hydroformylation. Insight into Detailed Mechanism

The Strong Acidity and the Process for Deprotonation of (η⁶-Toluene)Fe(H)₂(SiCl₃)₂

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Theoretical study of the hydroformylation reaction mechanism

Cited by 35 publications

References 22 publications

Mechanistic Insights into Hydroformylation Catalyzed by Cationic Cobalt(II) Complexes: In Silico Modification of the Catalyst System

Mechanistic Insights into Hydroformylation Catalyzed by Cationic Cobalt(II) Complexes: In Silico Modification of the Catalyst System

HCo(CO)3-Catalyzed Propene Hydroformylation. Insight into Detailed Mechanism

The Strong Acidity and the Process for Deprotonation of (η6-Toluene)Fe(H)2(SiCl3)2

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Product

Resources

About

HCo(CO)₃-Catalyzed Propene Hydroformylation. Insight into Detailed Mechanism

The Strong Acidity and the Process for Deprotonation of (η⁶-Toluene)Fe(H)₂(SiCl₃)₂