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Synthetic, structural, and solution thermochemical studies in the dimethylbis(phosphine)platinum(II) system : dichotomy between structural and thermodynamic trends

(1999) ORGANOMETALLICS. 18(4). p.474-479
Author
Organization
Abstract
Reaction enthalpies of the complex (COD)PtMe2 (COD = eta(4)-1,5-cyclooctadiene) with an extensive series of unidentate phosphines have been measured by solution calorimetry. The molecular structures of cis-P2PtMe2 for P = PEt3, PMe2Ph, P(pyrrolyl)(3), and PCy3 have been determined by single-crystal X-ray diffraction. The relative stabilities of the resulting P-2-PtMe2 complexes are strongly influenced by the size (cone angle) of the incoming phosphine, with larger cone angles resulting in less thermodynamically stable complexes. Crystallographic and P-31 NMR data, however, do not reflect the enthalpic stability scale and are more closely correlated to the electronic (chi) character of the phosphine ligands. The strength of the Pt-P interaction, as determined from these structural data, is greatest for phosphines with electron-withdrawing substituents, regardless of phosphine size or reaction enthalpy.
Keywords
N-PYRROLYL PHOSPHINES, PI-ACCEPTOR CHARACTER, LIGAND SUBSTITUTION, L(2)FE(CO)(3) SYSTEM, ENTHALPIES, COMPLEXES, CHEMISTRY

Citation

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MLA
Haar, CM, et al. “Synthetic, Structural, and Solution Thermochemical Studies in the Dimethylbis(Phosphine)Platinum(II) System : Dichotomy between Structural and Thermodynamic Trends.” ORGANOMETALLICS, vol. 18, no. 4, 1999, pp. 474–79.
APA
Haar, C., Nolan, S., Marshall, W., Moloy, K., Prock, A., & Giering, W. (1999). Synthetic, structural, and solution thermochemical studies in the dimethylbis(phosphine)platinum(II) system : dichotomy between structural and thermodynamic trends. ORGANOMETALLICS, 18(4), 474–479.
Chicago author-date
Haar, CM, Steven Nolan, WJ Marshall, KG Moloy, A Prock, and WP Giering. 1999. “Synthetic, Structural, and Solution Thermochemical Studies in the Dimethylbis(Phosphine)Platinum(II) System : Dichotomy between Structural and Thermodynamic Trends.” ORGANOMETALLICS 18 (4): 474–79.
Chicago author-date (all authors)
Haar, CM, Steven Nolan, WJ Marshall, KG Moloy, A Prock, and WP Giering. 1999. “Synthetic, Structural, and Solution Thermochemical Studies in the Dimethylbis(Phosphine)Platinum(II) System : Dichotomy between Structural and Thermodynamic Trends.” ORGANOMETALLICS 18 (4): 474–479.
Vancouver
1.
Haar C, Nolan S, Marshall W, Moloy K, Prock A, Giering W. Synthetic, structural, and solution thermochemical studies in the dimethylbis(phosphine)platinum(II) system : dichotomy between structural and thermodynamic trends. ORGANOMETALLICS. 1999;18(4):474–9.
IEEE
[1]
C. Haar, S. Nolan, W. Marshall, K. Moloy, A. Prock, and W. Giering, “Synthetic, structural, and solution thermochemical studies in the dimethylbis(phosphine)platinum(II) system : dichotomy between structural and thermodynamic trends,” ORGANOMETALLICS, vol. 18, no. 4, pp. 474–479, 1999.
@article{8170998,
  abstract     = {Reaction enthalpies of the complex (COD)PtMe2 (COD = eta(4)-1,5-cyclooctadiene) with an extensive series of unidentate phosphines have been measured by solution calorimetry. The molecular structures of cis-P2PtMe2 for P = PEt3, PMe2Ph, P(pyrrolyl)(3), and PCy3 have been determined by single-crystal X-ray diffraction. The relative stabilities of the resulting P-2-PtMe2 complexes are strongly influenced by the size (cone angle) of the incoming phosphine, with larger cone angles resulting in less thermodynamically stable complexes. Crystallographic and P-31 NMR data, however, do not reflect the enthalpic stability scale and are more closely correlated to the electronic (chi) character of the phosphine ligands. The strength of the Pt-P interaction, as determined from these structural data, is greatest for phosphines with electron-withdrawing substituents, regardless of phosphine size or reaction enthalpy.},
  author       = {Haar, CM and Nolan, Steven and Marshall, WJ and Moloy, KG and Prock, A and Giering, WP},
  issn         = {0276-7333},
  journal      = {ORGANOMETALLICS},
  keywords     = {N-PYRROLYL PHOSPHINES,PI-ACCEPTOR CHARACTER,LIGAND SUBSTITUTION,L(2)FE(CO)(3) SYSTEM,ENTHALPIES,COMPLEXES,CHEMISTRY},
  language     = {eng},
  number       = {4},
  pages        = {474--479},
  title        = {Synthetic, structural, and solution thermochemical studies in the dimethylbis(phosphine)platinum(II) system : dichotomy between structural and thermodynamic trends},
  url          = {http://dx.doi.org/10.1021/om9807001},
  volume       = {18},
  year         = {1999},
}

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