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Solution calorimetric investigation of oxidative addition of HEAr (E = O, S, Se; Ar = C6H4X, X = CH3, H, Cl, NO2) to (PMe3)4Ru(C2H4) : relationship between HEAr acidity and enthalpy of reaction

(1998) ORGANOMETALLICS. 17(16). p.3516-3521
Author
Organization
Abstract
The enthalpies of reactions of (PMe3)(4)Ru(C2H4) (1) with a series of HEAr compounds (E = O, S, Se; Ar = aryl), leading to the formation of (PMe3)(4)Ru(H)(EAr) complexes, have been measured by anaerobic solution calorimetry in C6H6 at 30.0 degrees C. These reactions are rapid and quantitative under the calorimetry conditions. The measured reaction enthalpies span a range of some 35 kcal/mol. The relative stability scale established is as follows: (PMe3)(4)Ru(H)(OC6H4-p-CH3) < (PMe3)(4)Ru(H)(OC6H5) < (PMe3)(4)Ru(H)(OC6H4-p-Cl) < (PMe3)(4)Ru(H)(OC6H4-p-NO2) < (PMe3)(4)Ru(H)(SC6H4-p-CH3) < (PMe3)(4)Ru(H)(SC6H5) < (PMe3)(4)Ru(H)(SC6H4-p-Cl) approximate to (PMe3)(4)Ru(H)(SeC6H5) < (PMe3)(4)Ru(H)(SC6H4-p-NO2). A single-crystal X-ray structure of one of these complexes, (PMe3)(4)Ru(SC6H5)H (7), is reported. The measured enthalpies of reaction display a dependence on the acidity of HEAr.
Keywords
TERTIARY PHOSPHINE-LIGANDS, ORGANORUTHENIUM THERMOCHEMISTRY, REDUCTIVE ELIMINATION, BOND STRENGTHS, N-H, METAL, COMPLEXES, BINDING, SUBSTITUTION, ALKOXIDES

Citation

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MLA
Huang, JK, et al. “Solution Calorimetric Investigation of Oxidative Addition of HEAr (E = O, S, Se; Ar = C6H4X, X = CH3, H, Cl, NO2) to (PMe3)4Ru(C2H4) : Relationship between HEAr Acidity and Enthalpy of Reaction.” ORGANOMETALLICS, vol. 17, no. 16, 1998, pp. 3516–21.
APA
Huang, J., Li, C., Nolan, S., & Petersen, J. (1998). Solution calorimetric investigation of oxidative addition of HEAr (E = O, S, Se; Ar = C6H4X, X = CH3, H, Cl, NO2) to (PMe3)4Ru(C2H4) : relationship between HEAr acidity and enthalpy of reaction. ORGANOMETALLICS, 17(16), 3516–3521.
Chicago author-date
Huang, JK, CB Li, Steven Nolan, and JL Petersen. 1998. “Solution Calorimetric Investigation of Oxidative Addition of HEAr (E = O, S, Se; Ar = C6H4X, X = CH3, H, Cl, NO2) to (PMe3)4Ru(C2H4) : Relationship between HEAr Acidity and Enthalpy of Reaction.” ORGANOMETALLICS 17 (16): 3516–21.
Chicago author-date (all authors)
Huang, JK, CB Li, Steven Nolan, and JL Petersen. 1998. “Solution Calorimetric Investigation of Oxidative Addition of HEAr (E = O, S, Se; Ar = C6H4X, X = CH3, H, Cl, NO2) to (PMe3)4Ru(C2H4) : Relationship between HEAr Acidity and Enthalpy of Reaction.” ORGANOMETALLICS 17 (16): 3516–3521.
Vancouver
1.
Huang J, Li C, Nolan S, Petersen J. Solution calorimetric investigation of oxidative addition of HEAr (E = O, S, Se; Ar = C6H4X, X = CH3, H, Cl, NO2) to (PMe3)4Ru(C2H4) : relationship between HEAr acidity and enthalpy of reaction. ORGANOMETALLICS. 1998;17(16):3516–21.
IEEE
[1]
J. Huang, C. Li, S. Nolan, and J. Petersen, “Solution calorimetric investigation of oxidative addition of HEAr (E = O, S, Se; Ar = C6H4X, X = CH3, H, Cl, NO2) to (PMe3)4Ru(C2H4) : relationship between HEAr acidity and enthalpy of reaction,” ORGANOMETALLICS, vol. 17, no. 16, pp. 3516–3521, 1998.
@article{8171068,
  abstract     = {The enthalpies of reactions of (PMe3)(4)Ru(C2H4) (1) with a series of HEAr compounds (E = O, S, Se; Ar = aryl), leading to the formation of (PMe3)(4)Ru(H)(EAr) complexes, have been measured by anaerobic solution calorimetry in C6H6 at 30.0 degrees C. These reactions are rapid and quantitative under the calorimetry conditions. The measured reaction enthalpies span a range of some 35 kcal/mol. The relative stability scale established is as follows: (PMe3)(4)Ru(H)(OC6H4-p-CH3) < (PMe3)(4)Ru(H)(OC6H5) < (PMe3)(4)Ru(H)(OC6H4-p-Cl) < (PMe3)(4)Ru(H)(OC6H4-p-NO2) < (PMe3)(4)Ru(H)(SC6H4-p-CH3) < (PMe3)(4)Ru(H)(SC6H5) < (PMe3)(4)Ru(H)(SC6H4-p-Cl) approximate to (PMe3)(4)Ru(H)(SeC6H5) < (PMe3)(4)Ru(H)(SC6H4-p-NO2). A single-crystal X-ray structure of one of these complexes, (PMe3)(4)Ru(SC6H5)H (7), is reported. The measured enthalpies of reaction display a dependence on the acidity of HEAr.},
  author       = {Huang, JK and Li, CB and Nolan, Steven and Petersen, JL},
  issn         = {0276-7333},
  journal      = {ORGANOMETALLICS},
  keywords     = {TERTIARY PHOSPHINE-LIGANDS,ORGANORUTHENIUM THERMOCHEMISTRY,REDUCTIVE ELIMINATION,BOND STRENGTHS,N-H,METAL,COMPLEXES,BINDING,SUBSTITUTION,ALKOXIDES},
  language     = {eng},
  number       = {16},
  pages        = {3516--3521},
  title        = {Solution calorimetric investigation of oxidative addition of HEAr (E = O, S, Se; Ar = C6H4X, X = CH3, H, Cl, NO2) to (PMe3)4Ru(C2H4) : relationship between HEAr acidity and enthalpy of reaction},
  url          = {http://dx.doi.org/10.1021/om980253p},
  volume       = {17},
  year         = {1998},
}

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