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Organoruthenium thermochemistry : absolute metal-ligand bond disruption enthalpies in the (η5-C5Me5)(CO)2Ru-X system (X = H, Cl, Br, I) and thermodynamic influences of ancillary ligand variation on the Ru-X bond disruption enthalpy

(1995) ORGANOMETALLICS. 14(3). p.1333-1338
Author
Organization
Abstract
The enthalpies of reaction of (eta(5)-C(5)Me(5))(CO)(2)RU-H (1) With CCl4, CBr4, and CH3I leading to the formation of (eta(5)-C(5)Me(5))(CO)(2)Ru-X complexes (X = Cl, Br, I) have been measured by solution calorimetry in THF at 30 degrees C. On the basis of enthalpies of reaction and the recently reported Ru-H in (C5H5)Ru(CO)(2)H (65 +/- 1.0 kcal/mol), an absolute Ru-X bond disruption enthalpy (BDE) scale can be established for ruthenium halide complexes. The absolute BDE scale for ruthenium halide complexes, (eta(5)-C(5)Me(5))(CO)(2)RU-X, is as follows (X, kcal/mol): Cl, 80.7; Br, 61.1; and I, 55.6, respectively. These ruthenium BDE values can be directly compared with other metal-based systems and lead to a clearer understanding of general BDE trends in M-X systems. In addition, a number of enthalpies of reaction were measured involving organoruthenium hydride complexes with varied ancillary ligands in order to examine the ancillary ligand effects on the relative Ru-X bond enthalpies.
Keywords
F-ELEMENT THERMOCHEMISTRY, ORGANOMETALLIC CHEMISTRY, PHOSPHORUS LIGANDS, PHOSPHINE-LIGANDS, BIDENTATE LIGANDS, COMPLEXES, HEATS, HYDROGEN, HYDRIDE, SUBSTITUTION

Citation

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MLA
Luo, L., et al. “Organoruthenium Thermochemistry : Absolute Metal-Ligand Bond Disruption Enthalpies in the (Η5-C5Me5)(CO)2Ru-X System (X = H, Cl, Br, I) and Thermodynamic Influences of Ancillary Ligand Variation on the Ru-X Bond Disruption Enthalpy.” ORGANOMETALLICS, vol. 14, no. 3, 1995, pp. 1333–38.
APA
Luo, L., Li, C., Cucullu, M., & Nolan, S. (1995). Organoruthenium thermochemistry : absolute metal-ligand bond disruption enthalpies in the (η5-C5Me5)(CO)2Ru-X system (X = H, Cl, Br, I) and thermodynamic influences of ancillary ligand variation on the Ru-X bond disruption enthalpy. ORGANOMETALLICS, 14(3), 1333–1338.
Chicago author-date
Luo, L, CB Li, ME Cucullu, and Steven Nolan. 1995. “Organoruthenium Thermochemistry : Absolute Metal-Ligand Bond Disruption Enthalpies in the (Η5-C5Me5)(CO)2Ru-X System (X = H, Cl, Br, I) and Thermodynamic Influences of Ancillary Ligand Variation on the Ru-X Bond Disruption Enthalpy.” ORGANOMETALLICS 14 (3): 1333–38.
Chicago author-date (all authors)
Luo, L, CB Li, ME Cucullu, and Steven Nolan. 1995. “Organoruthenium Thermochemistry : Absolute Metal-Ligand Bond Disruption Enthalpies in the (Η5-C5Me5)(CO)2Ru-X System (X = H, Cl, Br, I) and Thermodynamic Influences of Ancillary Ligand Variation on the Ru-X Bond Disruption Enthalpy.” ORGANOMETALLICS 14 (3): 1333–1338.
Vancouver
1.
Luo L, Li C, Cucullu M, Nolan S. Organoruthenium thermochemistry : absolute metal-ligand bond disruption enthalpies in the (η5-C5Me5)(CO)2Ru-X system (X = H, Cl, Br, I) and thermodynamic influences of ancillary ligand variation on the Ru-X bond disruption enthalpy. ORGANOMETALLICS. 1995;14(3):1333–8.
IEEE
[1]
L. Luo, C. Li, M. Cucullu, and S. Nolan, “Organoruthenium thermochemistry : absolute metal-ligand bond disruption enthalpies in the (η5-C5Me5)(CO)2Ru-X system (X = H, Cl, Br, I) and thermodynamic influences of ancillary ligand variation on the Ru-X bond disruption enthalpy,” ORGANOMETALLICS, vol. 14, no. 3, pp. 1333–1338, 1995.
@article{8171319,
  abstract     = {The enthalpies of reaction of (eta(5)-C(5)Me(5))(CO)(2)RU-H (1) With CCl4, CBr4, and CH3I leading to the formation of (eta(5)-C(5)Me(5))(CO)(2)Ru-X complexes (X = Cl, Br, I) have been measured by solution calorimetry in THF at 30 degrees C. On the basis of enthalpies of reaction and the recently reported Ru-H in (C5H5)Ru(CO)(2)H (65 +/- 1.0 kcal/mol), an absolute Ru-X bond disruption enthalpy (BDE) scale can be established for ruthenium halide complexes. The absolute BDE scale for ruthenium halide complexes, (eta(5)-C(5)Me(5))(CO)(2)RU-X, is as follows (X, kcal/mol): Cl, 80.7; Br, 61.1; and I, 55.6, respectively. These ruthenium BDE values can be directly compared with other metal-based systems and lead to a clearer understanding of general BDE trends in M-X systems. In addition, a number of enthalpies of reaction were measured involving organoruthenium hydride complexes with varied ancillary ligands in order to examine the ancillary ligand effects on the relative Ru-X bond enthalpies.},
  author       = {Luo, L and Li, CB and Cucullu, ME and Nolan, Steven},
  issn         = {0276-7333},
  journal      = {ORGANOMETALLICS},
  keywords     = {F-ELEMENT THERMOCHEMISTRY,ORGANOMETALLIC CHEMISTRY,PHOSPHORUS LIGANDS,PHOSPHINE-LIGANDS,BIDENTATE LIGANDS,COMPLEXES,HEATS,HYDROGEN,HYDRIDE,SUBSTITUTION},
  language     = {eng},
  number       = {3},
  pages        = {1333--1338},
  title        = {Organoruthenium thermochemistry : absolute metal-ligand bond disruption enthalpies in the (η5-C5Me5)(CO)2Ru-X system (X = H, Cl, Br, I) and thermodynamic influences of ancillary ligand variation on the Ru-X bond disruption enthalpy},
  url          = {http://dx.doi.org/10.1021/om00003a039},
  volume       = {14},
  year         = {1995},
}

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