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Enthalpies of reaction of (η5-C5H5)Ru(cyclooctadiene)Cl with tertiary phosphine ligands : ligand substitution as a gauge for metal basicity and a linear correlation of bond length and bond enthalpy

(1995) ORGANOMETALLICS. 14(1). p.289-296
Author
Organization
Abstract
The enthalpies of reaction of CpRu(COD)Cl (1) (Cp = eta(5)-C5H5; COD = cyclooctadiene) with a series of monodentate ligands, leading to the formation of CpRu(ER(3))(2)Cl (E = P, As), have been measured by anaerobic solution calorimetry in THF at 30.0 degrees C. These reactions are rapid and quantitatively lead to the formation of the corresponding CpRu(ER(3))(2)Cl complexes. The overall relative order of stability established for the preceding complexes is as follows: AsEt(3) < PPh(3) < PPh(2)Me < P(OPh)(3) < PEt(3) < P(n)Bu(3) < PPhMe(2) < PMe(3) < P(OMe)(3). Comparisons with other organometallic systems providing insights into factors influencing the Ru-L bond disruption enthalpies and metal basicity are discussed. Structural studies of two of these CpRu(ER(3))(2)Cl complexes (ER(3) = AsEt(3) (2) and PEt(3) (3)) have also been performed. Data for 2: monoclinic, C2/c; a = 30.549(5); b =. 10.523(2); c = 13.503(3) Angstrom; alpha gamma = 90 degrees; beta = 103.71(2)degrees; V = 4217.1 Angstrom(3); Z = 8; d(calcd) 2 = 1.656g cm(-1);n(obsd) 5328; R = 0.032. Data for 3: monoclinic, P2(1)/c; a 13.553(1); b = 8.283(2); c = 19.359(3) Angstrom; beta = 109.74(1)degrees; V = 2045.5 Angstrom 3; Z = 4; dcalcd = 1.422 g cm(-1); n(obsd) = 5152; R = 0.030. A relationship between bond distances and relative bond energies is made possible by the present data. This correlation is good and represents a rare example of such a relationship.
Keywords
CYCLOPENTADIENYL-OSMIUM CHEMISTRY, OPENING METATHESIS POLYMERIZATION, CATALYTIC ORGANOMETALLIC CHEMISTRY, F-ELEMENT THERMOCHEMISTRY, CP-ASTERISK-RU+, DISRUPTION ENTHALPIES, PHOSPHORUS LIGANDS, BIDENTATE LIGANDS, ORGANIC-SYNTHESIS, CARBENE COMPLEX

Citation

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MLA
Cucullu, ME, et al. “Enthalpies of Reaction of (Η5-C5H5)Ru(Cyclooctadiene)Cl with Tertiary Phosphine Ligands : Ligand Substitution as a Gauge for Metal Basicity and a Linear Correlation of Bond Length and Bond Enthalpy.” ORGANOMETALLICS, vol. 14, no. 1, 1995, pp. 289–96.
APA
Cucullu, M., Luo, L., Nolan, S., Fagan, P., Jones, N., & Calabrese, J. (1995). Enthalpies of reaction of (η5-C5H5)Ru(cyclooctadiene)Cl with tertiary phosphine ligands : ligand substitution as a gauge for metal basicity and a linear correlation of bond length and bond enthalpy. ORGANOMETALLICS, 14(1), 289–296.
Chicago author-date
Cucullu, ME, LB Luo, Steven Nolan, PJ Fagan, NL Jones, and JC Calabrese. 1995. “Enthalpies of Reaction of (Η5-C5H5)Ru(Cyclooctadiene)Cl with Tertiary Phosphine Ligands : Ligand Substitution as a Gauge for Metal Basicity and a Linear Correlation of Bond Length and Bond Enthalpy.” ORGANOMETALLICS 14 (1): 289–96.
Chicago author-date (all authors)
Cucullu, ME, LB Luo, Steven Nolan, PJ Fagan, NL Jones, and JC Calabrese. 1995. “Enthalpies of Reaction of (Η5-C5H5)Ru(Cyclooctadiene)Cl with Tertiary Phosphine Ligands : Ligand Substitution as a Gauge for Metal Basicity and a Linear Correlation of Bond Length and Bond Enthalpy.” ORGANOMETALLICS 14 (1): 289–296.
Vancouver
1.
Cucullu M, Luo L, Nolan S, Fagan P, Jones N, Calabrese J. Enthalpies of reaction of (η5-C5H5)Ru(cyclooctadiene)Cl with tertiary phosphine ligands : ligand substitution as a gauge for metal basicity and a linear correlation of bond length and bond enthalpy. ORGANOMETALLICS. 1995;14(1):289–96.
IEEE
[1]
M. Cucullu, L. Luo, S. Nolan, P. Fagan, N. Jones, and J. Calabrese, “Enthalpies of reaction of (η5-C5H5)Ru(cyclooctadiene)Cl with tertiary phosphine ligands : ligand substitution as a gauge for metal basicity and a linear correlation of bond length and bond enthalpy,” ORGANOMETALLICS, vol. 14, no. 1, pp. 289–296, 1995.
@article{8171328,
  abstract     = {The enthalpies of reaction of CpRu(COD)Cl (1) (Cp = eta(5)-C5H5; COD = cyclooctadiene) with a series of monodentate ligands, leading to the formation of CpRu(ER(3))(2)Cl (E = P, As), have been measured by anaerobic solution calorimetry in THF at 30.0 degrees C. These reactions are rapid and quantitatively lead to the formation of the corresponding CpRu(ER(3))(2)Cl complexes. The overall relative order of stability established for the preceding complexes is as follows: AsEt(3) < PPh(3) < PPh(2)Me < P(OPh)(3) < PEt(3) < P(n)Bu(3) < PPhMe(2) < PMe(3) < P(OMe)(3). Comparisons with other organometallic systems providing insights into factors influencing the Ru-L bond disruption enthalpies and metal basicity are discussed. Structural studies of two of these CpRu(ER(3))(2)Cl complexes (ER(3) = AsEt(3) (2) and PEt(3) (3)) have also been performed. Data for 2: monoclinic, C2/c; a = 30.549(5); b =. 10.523(2); c = 13.503(3) Angstrom; alpha gamma = 90 degrees; beta = 103.71(2)degrees; V = 4217.1 Angstrom(3); Z = 8; d(calcd) 2 = 1.656g cm(-1);n(obsd) 5328; R = 0.032. Data for 3: monoclinic, P2(1)/c; a 13.553(1); b = 8.283(2); c = 19.359(3) Angstrom; beta = 109.74(1)degrees; V = 2045.5 Angstrom 3; Z = 4; dcalcd = 1.422 g cm(-1); n(obsd) = 5152; R = 0.030. A relationship between bond distances and relative bond energies is made possible by the present data. This correlation is good and represents a rare example of such a relationship.},
  author       = {Cucullu, ME and Luo, LB and Nolan, Steven and Fagan, PJ and Jones, NL and Calabrese, JC},
  issn         = {0276-7333},
  journal      = {ORGANOMETALLICS},
  keywords     = {CYCLOPENTADIENYL-OSMIUM CHEMISTRY,OPENING METATHESIS POLYMERIZATION,CATALYTIC ORGANOMETALLIC CHEMISTRY,F-ELEMENT THERMOCHEMISTRY,CP-ASTERISK-RU+,DISRUPTION ENTHALPIES,PHOSPHORUS LIGANDS,BIDENTATE LIGANDS,ORGANIC-SYNTHESIS,CARBENE COMPLEX},
  language     = {eng},
  number       = {1},
  pages        = {289--296},
  title        = {Enthalpies of reaction of (η5-C5H5)Ru(cyclooctadiene)Cl with tertiary phosphine ligands : ligand substitution as a gauge for metal basicity and a linear correlation of bond length and bond enthalpy},
  url          = {http://dx.doi.org/10.1021/om00001a042},
  volume       = {14},
  year         = {1995},
}

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