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Effect of ancillary ligation on the relative bond disruption enthalpies of Ru-H and Ru-Cl bonds in Cp(PR3)2RuX (PR3 = PMe3, PMe2Ph, PMePh2, PPh3; X = H, Cl)

(2000) ORGANOMETALLICS. 19(23). p.4828-4833
Author
Organization
Abstract
The ruthenium chloride and hydride complexes Cp(PR3)(2)RuH {X = Cl; PR3 = PMe3 (1), PMe2Ph (2), PMePh2 (3), PPh3 (4); X = H; PR3 = PMe3 (5), PMe2Ph (6), PMePh2 (7), PPh3 (8)} were studied by spectroscopy and solution calorimetry. The structures of 2 and 3 are reported and complete the structural characterization of the series 1-4. In this series, the Ru-Cl distance (2.449 +/- 0.007 Angstrom) remains constant, while the Ru-PR3 distance increases in the order 1 < 2 < 3 < 4. The ruthenium hydrides 5-8 were prepared from the reaction of the corresponding ruthenium chloride with KOMe in methanol. Spectroscopic data on hydrides 5-8 indicated that the ruthenium hydride interaction decreases in the order 5 > 6 > 7 > 8. Enthalpies of reaction for the hydride/chloride metatheses of 5-8 with chlorocarbons (CHCl3 or CCl4) were studied by solution calorimetry and allowed for the determination of Ru-Cl bond disruption enthalpies (BDEs) relative to the corresponding Ru-H BDEs. [BDE(Ru-Cl) - BDE(Ru-H)] values covered a 6 kcal/mol range with an average of 21.4 +/- 2.5 kcal/mol. The magnitude of [BDE(Ru-Cl) - BDE(Ru-H)] correlated with the number of methyl groups on the phosphine and was dependent on the electronic and steric properties of the phosphine.
Keywords
RUTHENIUM SILYL COMPLEXES, LIGANDS, THERMOCHEMISTRY, HYDRIDE, CYCLOPENTADIENYL, CHEMISTRY, STRENGTHS, CATALYSIS, HEATS, CCL4

Citation

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MLA
Freeman, STN, et al. “Effect of Ancillary Ligation on the Relative Bond Disruption Enthalpies of Ru-H and Ru-Cl Bonds in Cp(PR3)2RuX (PR3 = PMe3, PMe2Ph, PMePh2, PPh3; X = H, Cl).” ORGANOMETALLICS, vol. 19, no. 23, 2000, pp. 4828–33.
APA
Freeman, S., Lemke, F., Haar, C., Nolan, S., & Petersen, J. (2000). Effect of ancillary ligation on the relative bond disruption enthalpies of Ru-H and Ru-Cl bonds in Cp(PR3)2RuX (PR3 = PMe3, PMe2Ph, PMePh2, PPh3; X = H, Cl). ORGANOMETALLICS, 19(23), 4828–4833.
Chicago author-date
Freeman, STN, FR Lemke, CM Haar, Steven Nolan, and JL Petersen. 2000. “Effect of Ancillary Ligation on the Relative Bond Disruption Enthalpies of Ru-H and Ru-Cl Bonds in Cp(PR3)2RuX (PR3 = PMe3, PMe2Ph, PMePh2, PPh3; X = H, Cl).” ORGANOMETALLICS 19 (23): 4828–33.
Chicago author-date (all authors)
Freeman, STN, FR Lemke, CM Haar, Steven Nolan, and JL Petersen. 2000. “Effect of Ancillary Ligation on the Relative Bond Disruption Enthalpies of Ru-H and Ru-Cl Bonds in Cp(PR3)2RuX (PR3 = PMe3, PMe2Ph, PMePh2, PPh3; X = H, Cl).” ORGANOMETALLICS 19 (23): 4828–4833.
Vancouver
1.
Freeman S, Lemke F, Haar C, Nolan S, Petersen J. Effect of ancillary ligation on the relative bond disruption enthalpies of Ru-H and Ru-Cl bonds in Cp(PR3)2RuX (PR3 = PMe3, PMe2Ph, PMePh2, PPh3; X = H, Cl). ORGANOMETALLICS. 2000;19(23):4828–33.
IEEE
[1]
S. Freeman, F. Lemke, C. Haar, S. Nolan, and J. Petersen, “Effect of ancillary ligation on the relative bond disruption enthalpies of Ru-H and Ru-Cl bonds in Cp(PR3)2RuX (PR3 = PMe3, PMe2Ph, PMePh2, PPh3; X = H, Cl),” ORGANOMETALLICS, vol. 19, no. 23, pp. 4828–4833, 2000.
@article{8170752,
  abstract     = {The ruthenium chloride and hydride complexes Cp(PR3)(2)RuH {X = Cl; PR3 = PMe3 (1), PMe2Ph (2), PMePh2 (3), PPh3 (4); X = H; PR3 = PMe3 (5), PMe2Ph (6), PMePh2 (7), PPh3 (8)} were studied by spectroscopy and solution calorimetry. The structures of 2 and 3 are reported and complete the structural characterization of the series 1-4. In this series, the Ru-Cl distance (2.449 +/- 0.007 Angstrom) remains constant, while the Ru-PR3 distance increases in the order 1 < 2 < 3 < 4. The ruthenium hydrides 5-8 were prepared from the reaction of the corresponding ruthenium chloride with KOMe in methanol. Spectroscopic data on hydrides 5-8 indicated that the ruthenium hydride interaction decreases in the order 5 > 6 > 7 > 8. Enthalpies of reaction for the hydride/chloride metatheses of 5-8 with chlorocarbons (CHCl3 or CCl4) were studied by solution calorimetry and allowed for the determination of Ru-Cl bond disruption enthalpies (BDEs) relative to the corresponding Ru-H BDEs. [BDE(Ru-Cl) - BDE(Ru-H)] values covered a 6 kcal/mol range with an average of 21.4 +/- 2.5 kcal/mol. The magnitude of [BDE(Ru-Cl) - BDE(Ru-H)] correlated with the number of methyl groups on the phosphine and was dependent on the electronic and steric properties of the phosphine.},
  author       = {Freeman, STN and Lemke, FR and Haar, CM and Nolan, Steven and Petersen, JL},
  issn         = {0276-7333},
  journal      = {ORGANOMETALLICS},
  keywords     = {RUTHENIUM SILYL COMPLEXES,LIGANDS,THERMOCHEMISTRY,HYDRIDE,CYCLOPENTADIENYL,CHEMISTRY,STRENGTHS,CATALYSIS,HEATS,CCL4},
  language     = {eng},
  number       = {23},
  pages        = {4828--4833},
  title        = {Effect of ancillary ligation on the relative bond disruption enthalpies of Ru-H and Ru-Cl bonds in Cp(PR3)2RuX (PR3 = PMe3, PMe2Ph, PMePh2, PPh3; X = H, Cl)},
  url          = {http://dx.doi.org/10.1021/om000420x},
  volume       = {19},
  year         = {2000},
}

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