Stereochemically Nonrigid Organometallic Molecules. XX. Proton Nuclear Magnetic Resonance Study of the Fluxional Behavior of Some Substituted (1,2,1-TrihaptobznzyY)-(pentahaptocyc\opentadienyl)dicarbonyl Compounds of Molybdenum and Tungsten

F. A. Cotton; Tobin J. Marks

doi:10.1021/ja01034a014

Stereochemically Nonrigid Organometallic Molecules. XX. Proton Nuclear Magnetic Resonance Study of the Fluxional Behavior of Some Substituted (1,2,1-TrihaptobznzyY)-(pentahaptocyc\opentadienyl)dicarbonyl Compounds of Molybdenum and Tungsten

F. A. Cotton, Tobin J. Marks

Chemistry

Research output: Contribution to journal › Article › peer-review

110 Scopus citations

Abstract

Several new fluxional molecules containing substituted 1,2,1-trihaptobenzyl groups bound to the (C₅H₅)Mo(CO)₂ and (C₅H₅)W(CO)₂ residues have been prepared and their proton magnetic resonance spectra studied with the objective of elucidating the pathway and evaluating the activation parameters concerned in the fluxional behavior of this class of molecules. The molecules are less difficult to prepare and more stable than previously reported. The chief qualitative conclusion, derived from the study of the 3,5-diisopropylbenzyl compound, is that the (C₅H₅)Mo(CO)₂ residue has access to all four equivalent (including enantiomorphically related) positions of attachment to the benzyl group. A plausible pathway would be via a monohapto- (i.e., σ-) C₆H₅CH₂MoiC₅H₅)(CO)₂ intermediate, in which rotation about the C₁-C₇ bond of the benzyl group can occur.

Original language	English (US)
Pages (from-to)	1339-1346
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	91
Issue number	6
DOIs	https://doi.org/10.1021/ja01034a014
State	Published - Mar 1969

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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Cotton, F. A., & Marks, T. J. (1969). Stereochemically Nonrigid Organometallic Molecules. XX. Proton Nuclear Magnetic Resonance Study of the Fluxional Behavior of Some Substituted (1,2,1-TrihaptobznzyY)-(pentahaptocyc\opentadienyl)dicarbonyl Compounds of Molybdenum and Tungsten. Journal of the American Chemical Society, 91(6), 1339-1346. https://doi.org/10.1021/ja01034a014

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title = "Stereochemically Nonrigid Organometallic Molecules. XX. Proton Nuclear Magnetic Resonance Study of the Fluxional Behavior of Some Substituted (1,2,1-TrihaptobznzyY)-(pentahaptocyc\opentadienyl)dicarbonyl Compounds of Molybdenum and Tungsten",

abstract = "Several new fluxional molecules containing substituted 1,2,1-trihaptobenzyl groups bound to the (C5H5)Mo(CO)2 and (C5H5)W(CO)2 residues have been prepared and their proton magnetic resonance spectra studied with the objective of elucidating the pathway and evaluating the activation parameters concerned in the fluxional behavior of this class of molecules. The molecules are less difficult to prepare and more stable than previously reported. The chief qualitative conclusion, derived from the study of the 3,5-diisopropylbenzyl compound, is that the (C5H5)Mo(CO)2 residue has access to all four equivalent (including enantiomorphically related) positions of attachment to the benzyl group. A plausible pathway would be via a monohapto- (i.e., σ-) C6H5CH2MoiC5H5)(CO)2 intermediate, in which rotation about the C1-C7 bond of the benzyl group can occur.",

author = "Cotton, {F. A.} and Marks, {Tobin J.}",

year = "1969",

month = mar,

doi = "10.1021/ja01034a014",

language = "English (US)",

volume = "91",

pages = "1339--1346",

journal = "Journal of the American Chemical Society",

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Cotton, FA & Marks, TJ 1969, 'Stereochemically Nonrigid Organometallic Molecules. XX. Proton Nuclear Magnetic Resonance Study of the Fluxional Behavior of Some Substituted (1,2,1-TrihaptobznzyY)-(pentahaptocyc\opentadienyl)dicarbonyl Compounds of Molybdenum and Tungsten', Journal of the American Chemical Society, vol. 91, no. 6, pp. 1339-1346. https://doi.org/10.1021/ja01034a014

Stereochemically Nonrigid Organometallic Molecules. XX. Proton Nuclear Magnetic Resonance Study of the Fluxional Behavior of Some Substituted (1,2,1-TrihaptobznzyY)-(pentahaptocyc\opentadienyl)dicarbonyl Compounds of Molybdenum and Tungsten. / Cotton, F. A.; Marks, Tobin J.
In: Journal of the American Chemical Society, Vol. 91, No. 6, 03.1969, p. 1339-1346.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Stereochemically Nonrigid Organometallic Molecules. XX. Proton Nuclear Magnetic Resonance Study of the Fluxional Behavior of Some Substituted (1,2,1-TrihaptobznzyY)-(pentahaptocyc\opentadienyl)dicarbonyl Compounds of Molybdenum and Tungsten

AU - Cotton, F. A.

AU - Marks, Tobin J.

PY - 1969/3

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N2 - Several new fluxional molecules containing substituted 1,2,1-trihaptobenzyl groups bound to the (C5H5)Mo(CO)2 and (C5H5)W(CO)2 residues have been prepared and their proton magnetic resonance spectra studied with the objective of elucidating the pathway and evaluating the activation parameters concerned in the fluxional behavior of this class of molecules. The molecules are less difficult to prepare and more stable than previously reported. The chief qualitative conclusion, derived from the study of the 3,5-diisopropylbenzyl compound, is that the (C5H5)Mo(CO)2 residue has access to all four equivalent (including enantiomorphically related) positions of attachment to the benzyl group. A plausible pathway would be via a monohapto- (i.e., σ-) C6H5CH2MoiC5H5)(CO)2 intermediate, in which rotation about the C1-C7 bond of the benzyl group can occur.

AB - Several new fluxional molecules containing substituted 1,2,1-trihaptobenzyl groups bound to the (C5H5)Mo(CO)2 and (C5H5)W(CO)2 residues have been prepared and their proton magnetic resonance spectra studied with the objective of elucidating the pathway and evaluating the activation parameters concerned in the fluxional behavior of this class of molecules. The molecules are less difficult to prepare and more stable than previously reported. The chief qualitative conclusion, derived from the study of the 3,5-diisopropylbenzyl compound, is that the (C5H5)Mo(CO)2 residue has access to all four equivalent (including enantiomorphically related) positions of attachment to the benzyl group. A plausible pathway would be via a monohapto- (i.e., σ-) C6H5CH2MoiC5H5)(CO)2 intermediate, in which rotation about the C1-C7 bond of the benzyl group can occur.

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Stereochemically Nonrigid Organometallic Molecules. XX. Proton Nuclear Magnetic Resonance Study of the Fluxional Behavior of Some Substituted (1,2,1-TrihaptobznzyY)-(pentahaptocyc\opentadienyl)dicarbonyl Compounds of Molybdenum and Tungsten

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