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Enthalpies of reaction of CpRu(COD)Cl (Cp = η5-C5H5; COD = cyclooctadiene) with chelating tertiary phosphine ligands : solution thermochemical investigation of ligand substitution and ring strain energies in CpRu(R2P(CH2)nPR2)Cl complexes

(1994) ORGANOMETALLICS. 13(9). p.3621-3627
Author
Organization
Abstract
The enthalpies of reaction of CpRu(COD)Cl (Cp = eta(5)-C5H5; COD = eta(4)-cyclooctadiene) with a series of bidentate ligands, leading to the formation of CpRu(PP)Cl complexes, have been measured by anaerobic solution calorimetry in THF at 30.0 degrees C. The overall relative order of stability established for these complexes is as follows: dppm < dmpm < dppb < dppe < dppp < dppv < depe < dmpe. Comparison between enthalpies of these reactions and those of monodentate phosphine ligands affords a quantitative treatment of ring strain enthalpies in these organoruthenium metallacyclic compounds. Significant ring strain energy is displayed in the four-membered metallacycle and is on the order of 13 kcal/mol. A single crystal X-ray diffraction study has been performed on one of the new complexes, CpRu(dppv)Cl [dppv = bis(diphenylphosphino)ethylene] (C31H27ClP2Ru.CH2Cl2, P1, a 10.344(2) Angstrom, b = 11.907(2) Angstrom, c 13.183(1) Angstrom, alpha 67.89(1)degrees, beta 76.52(1)degrees, gamma = 85.96(2)degrees, V = 1462.5(5) Angstrom(3), and Z = 2). Comparisons of the thermochemical data with the C(5)Me(5)-based system and related metallacyclic complexes are also presented.
Keywords
BOND DISRUPTION ENTHALPIES, F-ELEMENT THERMOCHEMISTRY, CATALYZED RECONSTITUTIVE CONDENSATION, TRANSITION-METAL HYDROGEN, CYCLOPENTADIENYL-RUTHENIUM, DISSOCIATION ENERGIES, CHEMISTRY, PENTAMETHYLCYCLOPENTADIENYL, ORGANORUTHENIUM, HYDROCARBYL

Citation

Please use this url to cite or link to this publication:

MLA
Li, CB, et al. “Enthalpies of Reaction of CpRu(COD)Cl (Cp = Η5-C5H5; COD = Cyclooctadiene) with Chelating Tertiary Phosphine Ligands : Solution Thermochemical Investigation of Ligand Substitution and Ring Strain Energies in CpRu(R2P(CH2)NPR2)Cl Complexes.” ORGANOMETALLICS, vol. 13, no. 9, 1994, pp. 3621–27.
APA
Li, C., Cucullu, M., McIntyre, R., Stevens, E., & Nolan, S. (1994). Enthalpies of reaction of CpRu(COD)Cl (Cp = η5-C5H5; COD = cyclooctadiene) with chelating tertiary phosphine ligands : solution thermochemical investigation of ligand substitution and ring strain energies in CpRu(R2P(CH2)nPR2)Cl complexes. ORGANOMETALLICS, 13(9), 3621–3627.
Chicago author-date
Li, CB, ME Cucullu, RA McIntyre, ED Stevens, and Steven Nolan. 1994. “Enthalpies of Reaction of CpRu(COD)Cl (Cp = Η5-C5H5; COD = Cyclooctadiene) with Chelating Tertiary Phosphine Ligands : Solution Thermochemical Investigation of Ligand Substitution and Ring Strain Energies in CpRu(R2P(CH2)NPR2)Cl Complexes.” ORGANOMETALLICS 13 (9): 3621–27.
Chicago author-date (all authors)
Li, CB, ME Cucullu, RA McIntyre, ED Stevens, and Steven Nolan. 1994. “Enthalpies of Reaction of CpRu(COD)Cl (Cp = Η5-C5H5; COD = Cyclooctadiene) with Chelating Tertiary Phosphine Ligands : Solution Thermochemical Investigation of Ligand Substitution and Ring Strain Energies in CpRu(R2P(CH2)NPR2)Cl Complexes.” ORGANOMETALLICS 13 (9): 3621–3627.
Vancouver
1.
Li C, Cucullu M, McIntyre R, Stevens E, Nolan S. Enthalpies of reaction of CpRu(COD)Cl (Cp = η5-C5H5; COD = cyclooctadiene) with chelating tertiary phosphine ligands : solution thermochemical investigation of ligand substitution and ring strain energies in CpRu(R2P(CH2)nPR2)Cl complexes. ORGANOMETALLICS. 1994;13(9):3621–7.
IEEE
[1]
C. Li, M. Cucullu, R. McIntyre, E. Stevens, and S. Nolan, “Enthalpies of reaction of CpRu(COD)Cl (Cp = η5-C5H5; COD = cyclooctadiene) with chelating tertiary phosphine ligands : solution thermochemical investigation of ligand substitution and ring strain energies in CpRu(R2P(CH2)nPR2)Cl complexes,” ORGANOMETALLICS, vol. 13, no. 9, pp. 3621–3627, 1994.
@article{8171345,
  abstract     = {The enthalpies of reaction of CpRu(COD)Cl (Cp = eta(5)-C5H5; COD = eta(4)-cyclooctadiene) with a series of bidentate ligands, leading to the formation of CpRu(PP)Cl complexes, have been measured by anaerobic solution calorimetry in THF at 30.0 degrees C. The overall relative order of stability established for these complexes is as follows: dppm < dmpm < dppb < dppe < dppp < dppv < depe < dmpe. Comparison between enthalpies of these reactions and those of monodentate phosphine ligands affords a quantitative treatment of ring strain enthalpies in these organoruthenium metallacyclic compounds. Significant ring strain energy is displayed in the four-membered metallacycle and is on the order of 13 kcal/mol. A single crystal X-ray diffraction study has been performed on one of the new complexes, CpRu(dppv)Cl [dppv = bis(diphenylphosphino)ethylene] (C31H27ClP2Ru.CH2Cl2, P1, a 10.344(2) Angstrom, b = 11.907(2) Angstrom, c 13.183(1) Angstrom, alpha 67.89(1)degrees, beta 76.52(1)degrees, gamma = 85.96(2)degrees, V = 1462.5(5) Angstrom(3), and Z = 2). Comparisons of the thermochemical data with the C(5)Me(5)-based system and related metallacyclic complexes are also presented.},
  author       = {Li, CB and Cucullu, ME and McIntyre, RA and Stevens, ED and Nolan, Steven},
  issn         = {0276-7333},
  journal      = {ORGANOMETALLICS},
  keywords     = {BOND DISRUPTION ENTHALPIES,F-ELEMENT THERMOCHEMISTRY,CATALYZED RECONSTITUTIVE CONDENSATION,TRANSITION-METAL HYDROGEN,CYCLOPENTADIENYL-RUTHENIUM,DISSOCIATION ENERGIES,CHEMISTRY,PENTAMETHYLCYCLOPENTADIENYL,ORGANORUTHENIUM,HYDROCARBYL},
  language     = {eng},
  number       = {9},
  pages        = {3621--3627},
  title        = {Enthalpies of reaction of CpRu(COD)Cl (Cp = η5-C5H5; COD = cyclooctadiene) with chelating tertiary phosphine ligands : solution thermochemical investigation of ligand substitution and ring strain energies in CpRu(R2P(CH2)nPR2)Cl complexes},
  url          = {http://dx.doi.org/10.1021/om00021a039},
  volume       = {13},
  year         = {1994},
}

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