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
- Author
- L Luo, CB Li, ME Cucullu and Steven Nolan (UGent)
- 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
Please use this url to cite or link to this publication: http://hdl.handle.net/1854/LU-8171319
- 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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