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Enthalpies of reaction of complex Cp*Ru(CH3CN)3+O3SCF3- (Cp* = η5-C5Me5) with arenes : solution thermochemical study of arene binding to the Cp*Ru+ fragment

(1992) ORGANOMETALLICS. 11(12). p.3947-3953
Author
Organization
Abstract
The enthalpies of reaction of Cp*Ru(CH3CN)3OTf (Cp* = eta5-C5(CH3)5, OTf = O3SCF3) with a series of arenes have been measured by solution calorimetry. The results of this study are used to establish the following relative stability scale leading to the formation of Cp*Ru(arene)OTf complexes in THF (in kcal/mol): naphthalene, -1.7 +/- 0.1; benzene, -3.4 +/- 0.1; biphenyl, -3.6 +/- 0.1; toluene, -4.3 +/- 0.2; p-xylene, -4.6 +/- 0.2; (trimethylsilyl)benzene, -5.0 +/- 0.2; anisole, -5.4 +/- 0.2; mesitylene, -5.5 +/- 0.1; indole, -7.3 +/-0.2; NN-dimethylaniline, -7.5 +/- 0.1; p-bis(dimethylamino)benzene, -8.3 +/- 0.2. The solid-state structure of one of these arene complexes, Cp*Ru[C6H5(Si(CH3)3)]OTf, was determined by a low-temperature data collection X-ray crystallographic study. This investigation illustrates the presence of steric interactions between the phenyl TMS methyl groups and the Cp* methyl group and explains the small measured enthalpy of reaction. The enthalpies of arene substitution from Cp*Ru(CH3CN)3OTf span some 6.6 kcal/mol and vary as a function of the electron-donating ability of the arene. Factors affecting the Ru-arene bond energy are discussed, and thermodynamic comparisons with other organometallic systems are presented.
Keywords
BOND DISRUPTION ENTHALPIES, F-ELEMENT THERMOCHEMISTRY, DISPLACEMENT-REACTIONS, LIGAND SUBSTITUTION, INSERTION REACTION, CARBON-MONOXIDE, CO-INSERTION, COMPLEXES, METAL, HYDROGEN

Citation

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MLA
Nolan, Steven, et al. “Enthalpies of Reaction of Complex Cp*Ru(CH3CN)3+O3SCF3- (Cp* = Η5-C5Me5) with Arenes : Solution Thermochemical Study of Arene Binding to the Cp*Ru+ Fragment.” ORGANOMETALLICS, vol. 11, no. 12, 1992, pp. 3947–53.
APA
Nolan, S., Martin, K., Stevens, E., & Fagan, P. (1992). Enthalpies of reaction of complex Cp*Ru(CH3CN)3+O3SCF3- (Cp* = η5-C5Me5) with arenes : solution thermochemical study of arene binding to the Cp*Ru+ fragment. ORGANOMETALLICS, 11(12), 3947–3953.
Chicago author-date
Nolan, Steven, KL Martin, ED Stevens, and PJ Fagan. 1992. “Enthalpies of Reaction of Complex Cp*Ru(CH3CN)3+O3SCF3- (Cp* = Η5-C5Me5) with Arenes : Solution Thermochemical Study of Arene Binding to the Cp*Ru+ Fragment.” ORGANOMETALLICS 11 (12): 3947–53.
Chicago author-date (all authors)
Nolan, Steven, KL Martin, ED Stevens, and PJ Fagan. 1992. “Enthalpies of Reaction of Complex Cp*Ru(CH3CN)3+O3SCF3- (Cp* = Η5-C5Me5) with Arenes : Solution Thermochemical Study of Arene Binding to the Cp*Ru+ Fragment.” ORGANOMETALLICS 11 (12): 3947–3953.
Vancouver
1.
Nolan S, Martin K, Stevens E, Fagan P. Enthalpies of reaction of complex Cp*Ru(CH3CN)3+O3SCF3- (Cp* = η5-C5Me5) with arenes : solution thermochemical study of arene binding to the Cp*Ru+ fragment. ORGANOMETALLICS. 1992;11(12):3947–53.
IEEE
[1]
S. Nolan, K. Martin, E. Stevens, and P. Fagan, “Enthalpies of reaction of complex Cp*Ru(CH3CN)3+O3SCF3- (Cp* = η5-C5Me5) with arenes : solution thermochemical study of arene binding to the Cp*Ru+ fragment,” ORGANOMETALLICS, vol. 11, no. 12, pp. 3947–3953, 1992.
@article{8171447,
  abstract     = {The enthalpies of reaction of Cp*Ru(CH3CN)3OTf (Cp* = eta5-C5(CH3)5, OTf = O3SCF3) with a series of arenes have been measured by solution calorimetry. The results of this study are used to establish the following relative stability scale leading to the formation of Cp*Ru(arene)OTf complexes in THF (in kcal/mol): naphthalene, -1.7 +/- 0.1; benzene, -3.4 +/- 0.1; biphenyl, -3.6 +/- 0.1; toluene, -4.3 +/- 0.2; p-xylene, -4.6 +/- 0.2; (trimethylsilyl)benzene, -5.0 +/- 0.2; anisole, -5.4 +/- 0.2; mesitylene, -5.5 +/- 0.1; indole, -7.3 +/-0.2; NN-dimethylaniline, -7.5 +/- 0.1; p-bis(dimethylamino)benzene, -8.3 +/- 0.2. The solid-state structure of one of these arene complexes, Cp*Ru[C6H5(Si(CH3)3)]OTf, was determined by a low-temperature data collection X-ray crystallographic study. This investigation illustrates the presence of steric interactions between the phenyl TMS methyl groups and the Cp* methyl group and explains the small measured enthalpy of reaction. The enthalpies of arene substitution from Cp*Ru(CH3CN)3OTf span some 6.6 kcal/mol and vary as a function of the electron-donating ability of the arene. Factors affecting the Ru-arene bond energy are discussed, and thermodynamic comparisons with other organometallic systems are presented.},
  author       = {Nolan, Steven and Martin, KL and Stevens, ED and Fagan, PJ},
  issn         = {0276-7333},
  journal      = {ORGANOMETALLICS},
  keywords     = {BOND DISRUPTION ENTHALPIES,F-ELEMENT THERMOCHEMISTRY,DISPLACEMENT-REACTIONS,LIGAND SUBSTITUTION,INSERTION REACTION,CARBON-MONOXIDE,CO-INSERTION,COMPLEXES,METAL,HYDROGEN},
  language     = {eng},
  number       = {12},
  pages        = {3947--3953},
  title        = {Enthalpies of reaction of complex Cp*Ru(CH3CN)3+O3SCF3- (Cp* = η5-C5Me5) with arenes : solution thermochemical study of arene binding to the Cp*Ru+ fragment},
  url          = {http://dx.doi.org/10.1021/om00060a008},
  volume       = {11},
  year         = {1992},
}

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