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Organoruthenium thermochemistry : enthalpies of reaction of (Cp*RuCl)4 and Cp*Ru(COD)Cl (Cp* = η5-C5Me5, COD = cyclooctadiene) with dienes and tertiary phosphine ligands

L Luo, Steven Nolan (UGent) and PJ Fagan
(1993) ORGANOMETALLICS. 12(11). p.4305-4311
Author
Organization
Abstract
The enthalpies of reaction of Cp*Ru(COD)Cl(Cp* = eta5-C5Me5, COD = cyclooctadiene) with a series of monodentate ligands, leading to the formation of Cp*Ru(ER3)2Cl (E = P, As), have been measured by anaerobic solution calorimetry in THF at 30-degrees-C. The enthalpies of reaction associated with the rapid and quantitative reaction of the (Cp*RuCl)4 complex with diene ligands in THF at 30-degrees-C, producing Cp*Ru(diene)CI complexes, have also been investigated. Reaction of (Cp*RuCl)4 with excess phosphine ligand, at 30-degrees-C, has been shown to quantitatively yield the corresponding Cp*Ru(PR3)2Cl complex and allows for the design of a thermochemical cycle assuring the internal consistency of the thermochemical data. The overall relative order of stability established for the preceding complexes is as follows: for monodentate ligands, AsEt3 < PPh3 < PnBu3 < PEt3 < PPh2Me < P(OPh)3 < PPhMe2 < PMe3 < P(OMe)3; for dienes, 2,3-dimethyl-1,3-butadiene < 1,3-cyclohexadiene < cyclooctadiene < 1,3-pentadiene < norbornadiene. Comparisons with other organometallic systems and insight into factors influencing the Ru-L bond disruption enthalpies are discussed.
Keywords
BOND DISRUPTION ENTHALPIES, TRANSITION-METAL HYDROGEN, F-ELEMENT THERMOCHEMISTRY, ORGANOMETALLIC CHEMISTRY, DISSOCIATION ENERGIES, HOMOGENEOUS CATALYSIS, PHOSPHORUS LIGANDS, ORGANIC-SYNTHESIS, COMPLEXES, CYCLOPENTADIENYL

Citation

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Chicago
Luo, L, Steven Nolan, and PJ Fagan. 1993. “Organoruthenium Thermochemistry : Enthalpies of Reaction of (Cp*RuCl)4 and Cp*Ru(COD)Cl (Cp* = η5-C5Me5, COD = Cyclooctadiene) with Dienes and Tertiary Phosphine Ligands.” Organometallics 12 (11): 4305–4311.
APA
Luo, L, Nolan, S., & Fagan, P. (1993). Organoruthenium thermochemistry : enthalpies of reaction of (Cp*RuCl)4 and Cp*Ru(COD)Cl (Cp* = η5-C5Me5, COD = cyclooctadiene) with dienes and tertiary phosphine ligands. ORGANOMETALLICS, 12(11), 4305–4311.
Vancouver
1.
Luo L, Nolan S, Fagan P. Organoruthenium thermochemistry : enthalpies of reaction of (Cp*RuCl)4 and Cp*Ru(COD)Cl (Cp* = η5-C5Me5, COD = cyclooctadiene) with dienes and tertiary phosphine ligands. ORGANOMETALLICS. 1993;12(11):4305–11.
MLA
Luo, L, Steven Nolan, and PJ Fagan. “Organoruthenium Thermochemistry : Enthalpies of Reaction of (Cp*RuCl)4 and Cp*Ru(COD)Cl (Cp* = η5-C5Me5, COD = Cyclooctadiene) with Dienes and Tertiary Phosphine Ligands.” ORGANOMETALLICS 12.11 (1993): 4305–4311. Print.
@article{8171418,
  abstract     = {The enthalpies of reaction of Cp*Ru(COD)Cl(Cp* = eta5-C5Me5, COD = cyclooctadiene) with a series of monodentate ligands, leading to the formation of Cp*Ru(ER3)2Cl (E = P, As), have been measured by anaerobic solution calorimetry in THF at 30-degrees-C. The enthalpies of reaction associated with the rapid and quantitative reaction of the (Cp*RuCl)4 complex with diene ligands in THF at 30-degrees-C, producing Cp*Ru(diene)CI complexes, have also been investigated. Reaction of (Cp*RuCl)4 with excess phosphine ligand, at 30-degrees-C, has been shown to quantitatively yield the corresponding Cp*Ru(PR3)2Cl complex and allows for the design of a thermochemical cycle assuring the internal consistency of the thermochemical data. The overall relative order of stability established for the preceding complexes is as follows: for monodentate ligands, AsEt3 {\textlangle} PPh3 {\textlangle} PnBu3 {\textlangle} PEt3 {\textlangle} PPh2Me {\textlangle} P(OPh)3 {\textlangle} PPhMe2 {\textlangle} PMe3 {\textlangle} P(OMe)3; for dienes, 2,3-dimethyl-1,3-butadiene {\textlangle} 1,3-cyclohexadiene {\textlangle} cyclooctadiene {\textlangle} 1,3-pentadiene {\textlangle} norbornadiene. Comparisons with other organometallic systems and insight into factors influencing the Ru-L bond disruption enthalpies are discussed.},
  author       = {Luo, L and Nolan, Steven and Fagan, PJ},
  issn         = {0276-7333},
  journal      = {ORGANOMETALLICS},
  language     = {eng},
  number       = {11},
  pages        = {4305--4311},
  title        = {Organoruthenium thermochemistry : enthalpies of reaction of (Cp*RuCl)4 and Cp*Ru(COD)Cl (Cp* = \ensuremath{\eta}5-C5Me5, COD = cyclooctadiene) with dienes and tertiary phosphine ligands},
  url          = {http://dx.doi.org/10.1021/om00035a015},
  volume       = {12},
  year         = {1993},
}

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