Mechanism of olefin rearrangements induced by iron carbonyls. Rearrangements in the bicyclo[6.1.0]nonene system

Barborak, James C.; Dasher, Luther W.; McPhail, Andrew T.; Nichols, J. B.; Onan, Kay D.

doi:10.1021/ic50188a049

Cited by 14 publications

(1 citation statement)

References 15 publications

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“…Iron pentacarbonyl (IPC) has been widely used in conjunction with ultraviolet (UV) light to catalyze a number of alkene isomerization reactions . The exact mechanisms for these reactions have been studied through computational, static, and ultrafast experimental techniques . These studies all suggest that formation of the key intermediate Fe(CO) 3 ●(η 2 ‐alkene) is necessary to induce the hydride shift leading to isomerization.…”

Section: Introductionmentioning

confidence: 99%

Combined ¹ H NMR and DFT study of the solvent effects on the iron pentacarbonyl-catalyzed photo-assisted isomerization of allyl alcohol

Chase

McDonough

Overly

et al. 2013

J. Phys. Org. Chem.

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The relative rates of iron pentacarbonyl‐catalyzed photo‐induced isomerization of allyl alcohol to propanal in various solvents have been measured using 1H NMR spectroscopy. The reactions were run in linear and cyclic alkanes, alcohols, and amines in order to investigate solvent effects on the isomerization mechanism upon ultraviolet irradiation. The isomerization was efficient in nonane, hexane, cyclohexane, and benzene. The isomerization was very slow or completely suppressed in ethanol, propanol, isopropanol, triethylamine, and pyridine. Density functional theory calculations predicted thermodynamically favorable (ΔGo < 0) formation of Fe(CO)4–solvent compounds in the suppressing alcohol/amine solvents and unfavorable (ΔGo > 0) formation in the hydrocarbon solvents. The strong solvent ligation likely prevents formation of Fe(CO)3●(η2‐alkene) necessary for isomerization. Copyright © 2013 John Wiley & Sons, Ltd.

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Section: Introductionmentioning

confidence: 99%

Combined ¹ H NMR and DFT study of the solvent effects on the iron pentacarbonyl-catalyzed photo-assisted isomerization of allyl alcohol

Chase

McDonough

Overly

et al. 2013

J. Phys. Org. Chem.

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ChemInform Abstract: MECHANISM OF OLEFIN REARRANGEMENTS INDUCED BY IRON CARBONYLS. REARRANGEMENTS IN THE BICYCLO(6.1.0)NONENE SYSTEM

Barborak¹,

Dasher²,

McPhail³

et al. 1979

Chemischer Informationsdienst

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Über die Temperaturabhängigkeit der ¹³C‐NMR.‐Spektren von Tetracarbonyl (η‐(Z)‐cycloocten)eisen und (Z)‐cycloocten

Büren

Cosandey

Hansen

1980

Helvetica Chimica Acta

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On the Temperature Dependence of the I3C-NMR.-Spectra of Tetracarbonyl(q-(a-cyc1ooctene)iron and of (a-Cyclooctene SummaryReaction of (Z)-cyclooctene (1) with Fe2(CO)9 in pentane at 0" yielded tetracarbonyl(q-(Z)-cyc1ooctene)iron (2) as a yellow oil which can be stored over a longer period only at -78 '.It is shown that the title compounds (1 and 2, respectively) are fluxional. The activation parameters for the conformational C-atom site exchange of (Z)-cyclooctene (1) and tetracarbonyl (q-(Z)-cyc1ooctene)iron (2) (in CC12F2) have been determined between 113 K and 151 K for 1 and between 151 K and 205 K for 2, respectively, by a complete line shape analysis of the temperature dependent proton noise-decoupled 13C-NMR. signals of the olefinic C-atom. The kinetic data and activation parameters are given in Tables I and 2.

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Mechanism of olefin rearrangements induced by iron carbonyls. Rearrangements in the bicyclo[6.1.0]nonene system

Cited by 14 publications

References 15 publications

Combined ¹ H NMR and DFT study of the solvent effects on the iron pentacarbonyl-catalyzed photo-assisted isomerization of allyl alcohol

Combined ¹ H NMR and DFT study of the solvent effects on the iron pentacarbonyl-catalyzed photo-assisted isomerization of allyl alcohol

ChemInform Abstract: MECHANISM OF OLEFIN REARRANGEMENTS INDUCED BY IRON CARBONYLS. REARRANGEMENTS IN THE BICYCLO(6.1.0)NONENE SYSTEM

Über die Temperaturabhängigkeit der ¹³C‐NMR.‐Spektren von Tetracarbonyl (η‐(Z)‐cycloocten)eisen und (Z)‐cycloocten

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Mechanism of olefin rearrangements induced by iron carbonyls. Rearrangements in the bicyclo[6.1.0]nonene system

Cited by 14 publications

References 15 publications

Combined 1 H NMR and DFT study of the solvent effects on the iron pentacarbonyl-catalyzed photo-assisted isomerization of allyl alcohol

Combined 1 H NMR and DFT study of the solvent effects on the iron pentacarbonyl-catalyzed photo-assisted isomerization of allyl alcohol

ChemInform Abstract: MECHANISM OF OLEFIN REARRANGEMENTS INDUCED BY IRON CARBONYLS. REARRANGEMENTS IN THE BICYCLO(6.1.0)NONENE SYSTEM

Über die Temperaturabhängigkeit der 13C‐NMR.‐Spektren von Tetracarbonyl (η‐(Z)‐cycloocten)eisen und (Z)‐cycloocten

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Combined ¹ H NMR and DFT study of the solvent effects on the iron pentacarbonyl-catalyzed photo-assisted isomerization of allyl alcohol

Combined ¹ H NMR and DFT study of the solvent effects on the iron pentacarbonyl-catalyzed photo-assisted isomerization of allyl alcohol

Über die Temperaturabhängigkeit der ¹³C‐NMR.‐Spektren von Tetracarbonyl (η‐(Z)‐cycloocten)eisen und (Z)‐cycloocten