Stereochemically nonrigid organometallic molecules. XXIV. Preparation and nuclear magnetic resonance study of some fluxional cyclooctatetraene derivatives of ruthenium carbonyl

F. A. Cotton, A. Davison, Tobin J Marks, A. Musco

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Abstract

The preparation and characterization of four fluxional organometallic molecules derived from the reaction of Ru3(CO)12 with cyclooctatetraene are reported. The molecules are C8H8Ru(CO)3, C8H8Ru2(CO)6, C8H8-Ru2(CO)5, and (C8H8)2Ru3(CO)4. The limiting low-temperature pmr spectrum of C8H8Ru(CO)3 has been observed at about -140° and shows that the instantaneous structure is of the 1,2,3,4-tetrahapto type. The qualitative nature of the line-shape changes at intermediate temperatures shows that rearrangement takes place mainly by 1,2 shifts. Detailed analysis using computer-simulated spectra confirms this and enables us to set an upper limit of about 30% on the occurrence of 1,3 or other shift processes. The Arrhenius activation energy is 9.4 ± 0.5 kcal/mol. For C8H8Ru2(CO)6 the pmr spectrum has been recorded down to -120°. The limiting low-temperature spectrum confirms that the dissymmetric structure previously observed (Cotton and Edwards) in the crystalline substance persists as the instantaneous structure in solution. Spin-decoupling experiments on the room-temperature pmr spectrum show that a time-average mirror plane exists. These results, along with the changes observed in the spectra at intermediate temperatures, are interpreted in terms of an oscillation of the (OC)3Ru-Ru(CO)3 group relative to the C8H8 ring such that the enantiomers are rapidly interconverted at room temperature. C8H8Ru2-(CO)6 readily loses CO at higher temperatures giving C8H8Ru2(CO)5, This is a fluxional molecule (single, sharp proton line at 25°) presumably isostructural with C8H8Fe2(CO)5. Because of its very low solubility at lower temperatures efforts to observe a limiting low-temperature spectrum have failed. The preparation and characterization of (C8H8)2Ru3(CO)4 are fully described. This fluxional molecule has also failed to yield a low-temperature spectrum because of a severe solubility problem.

Original languageEnglish
Pages (from-to)6598-6603
Number of pages6
JournalJournal of the American Chemical Society
Volume91
Issue number24
Publication statusPublished - 1969

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Ruthenium
Organometallics
Carbon Monoxide
Magnetic Resonance Spectroscopy
Nuclear magnetic resonance
Derivatives
Molecules
Temperature
Solubility
Enantiomers
Cotton
Protons
Mirrors
Activation energy
Crystalline materials

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{29341801e32d469ba0aa32c78d372845,
title = "Stereochemically nonrigid organometallic molecules. XXIV. Preparation and nuclear magnetic resonance study of some fluxional cyclooctatetraene derivatives of ruthenium carbonyl",
abstract = "The preparation and characterization of four fluxional organometallic molecules derived from the reaction of Ru3(CO)12 with cyclooctatetraene are reported. The molecules are C8H8Ru(CO)3, C8H8Ru2(CO)6, C8H8-Ru2(CO)5, and (C8H8)2Ru3(CO)4. The limiting low-temperature pmr spectrum of C8H8Ru(CO)3 has been observed at about -140° and shows that the instantaneous structure is of the 1,2,3,4-tetrahapto type. The qualitative nature of the line-shape changes at intermediate temperatures shows that rearrangement takes place mainly by 1,2 shifts. Detailed analysis using computer-simulated spectra confirms this and enables us to set an upper limit of about 30{\%} on the occurrence of 1,3 or other shift processes. The Arrhenius activation energy is 9.4 ± 0.5 kcal/mol. For C8H8Ru2(CO)6 the pmr spectrum has been recorded down to -120°. The limiting low-temperature spectrum confirms that the dissymmetric structure previously observed (Cotton and Edwards) in the crystalline substance persists as the instantaneous structure in solution. Spin-decoupling experiments on the room-temperature pmr spectrum show that a time-average mirror plane exists. These results, along with the changes observed in the spectra at intermediate temperatures, are interpreted in terms of an oscillation of the (OC)3Ru-Ru(CO)3 group relative to the C8H8 ring such that the enantiomers are rapidly interconverted at room temperature. C8H8Ru2-(CO)6 readily loses CO at higher temperatures giving C8H8Ru2(CO)5, This is a fluxional molecule (single, sharp proton line at 25°) presumably isostructural with C8H8Fe2(CO)5. Because of its very low solubility at lower temperatures efforts to observe a limiting low-temperature spectrum have failed. The preparation and characterization of (C8H8)2Ru3(CO)4 are fully described. This fluxional molecule has also failed to yield a low-temperature spectrum because of a severe solubility problem.",
author = "Cotton, {F. A.} and A. Davison and Marks, {Tobin J} and A. Musco",
year = "1969",
language = "English",
volume = "91",
pages = "6598--6603",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "24",

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T1 - Stereochemically nonrigid organometallic molecules. XXIV. Preparation and nuclear magnetic resonance study of some fluxional cyclooctatetraene derivatives of ruthenium carbonyl

AU - Cotton, F. A.

AU - Davison, A.

AU - Marks, Tobin J

AU - Musco, A.

PY - 1969

Y1 - 1969

N2 - The preparation and characterization of four fluxional organometallic molecules derived from the reaction of Ru3(CO)12 with cyclooctatetraene are reported. The molecules are C8H8Ru(CO)3, C8H8Ru2(CO)6, C8H8-Ru2(CO)5, and (C8H8)2Ru3(CO)4. The limiting low-temperature pmr spectrum of C8H8Ru(CO)3 has been observed at about -140° and shows that the instantaneous structure is of the 1,2,3,4-tetrahapto type. The qualitative nature of the line-shape changes at intermediate temperatures shows that rearrangement takes place mainly by 1,2 shifts. Detailed analysis using computer-simulated spectra confirms this and enables us to set an upper limit of about 30% on the occurrence of 1,3 or other shift processes. The Arrhenius activation energy is 9.4 ± 0.5 kcal/mol. For C8H8Ru2(CO)6 the pmr spectrum has been recorded down to -120°. The limiting low-temperature spectrum confirms that the dissymmetric structure previously observed (Cotton and Edwards) in the crystalline substance persists as the instantaneous structure in solution. Spin-decoupling experiments on the room-temperature pmr spectrum show that a time-average mirror plane exists. These results, along with the changes observed in the spectra at intermediate temperatures, are interpreted in terms of an oscillation of the (OC)3Ru-Ru(CO)3 group relative to the C8H8 ring such that the enantiomers are rapidly interconverted at room temperature. C8H8Ru2-(CO)6 readily loses CO at higher temperatures giving C8H8Ru2(CO)5, This is a fluxional molecule (single, sharp proton line at 25°) presumably isostructural with C8H8Fe2(CO)5. Because of its very low solubility at lower temperatures efforts to observe a limiting low-temperature spectrum have failed. The preparation and characterization of (C8H8)2Ru3(CO)4 are fully described. This fluxional molecule has also failed to yield a low-temperature spectrum because of a severe solubility problem.

AB - The preparation and characterization of four fluxional organometallic molecules derived from the reaction of Ru3(CO)12 with cyclooctatetraene are reported. The molecules are C8H8Ru(CO)3, C8H8Ru2(CO)6, C8H8-Ru2(CO)5, and (C8H8)2Ru3(CO)4. The limiting low-temperature pmr spectrum of C8H8Ru(CO)3 has been observed at about -140° and shows that the instantaneous structure is of the 1,2,3,4-tetrahapto type. The qualitative nature of the line-shape changes at intermediate temperatures shows that rearrangement takes place mainly by 1,2 shifts. Detailed analysis using computer-simulated spectra confirms this and enables us to set an upper limit of about 30% on the occurrence of 1,3 or other shift processes. The Arrhenius activation energy is 9.4 ± 0.5 kcal/mol. For C8H8Ru2(CO)6 the pmr spectrum has been recorded down to -120°. The limiting low-temperature spectrum confirms that the dissymmetric structure previously observed (Cotton and Edwards) in the crystalline substance persists as the instantaneous structure in solution. Spin-decoupling experiments on the room-temperature pmr spectrum show that a time-average mirror plane exists. These results, along with the changes observed in the spectra at intermediate temperatures, are interpreted in terms of an oscillation of the (OC)3Ru-Ru(CO)3 group relative to the C8H8 ring such that the enantiomers are rapidly interconverted at room temperature. C8H8Ru2-(CO)6 readily loses CO at higher temperatures giving C8H8Ru2(CO)5, This is a fluxional molecule (single, sharp proton line at 25°) presumably isostructural with C8H8Fe2(CO)5. Because of its very low solubility at lower temperatures efforts to observe a limiting low-temperature spectrum have failed. The preparation and characterization of (C8H8)2Ru3(CO)4 are fully described. This fluxional molecule has also failed to yield a low-temperature spectrum because of a severe solubility problem.

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