Ground-state versus transition-state effects in arene displacement reactions of the complexes (η6-arene)Cr(CO)s

Linear dependence of transition-state energies and resonance energies of the arene ligands

Songshen Zhang, Jian Kun Shen, Fred Basolo, Telvin D. Ju, Russell F. Lang, Gabor Kiss, Carl Hoff

Research output: Contribution to journalArticle

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Abstract

The rates of displacement of arene and thiophene ligands by P(n-Bu)3 in decalin and PPh3 in toluene have been studied. The reactions are first order in complex and incoming ligand. Rates of reaction increase in the order benzene < styrene < triphenylene < pyrene < phenanthrene < dimethylthiophene < naphthalene < thiophene < anthracene and span roughly 8 orders of magnitude. The thermodynamic stability of these species has also been investigated by solution calorimetry and equilibrium studies. The order of decreasing thermodynamic stability is benzene > dimethylthiophene > triphenylene > phenanthrene > thiophene > naphthalene > anthracene > pyrene and spans about 7 kcal/mol. The combination of kinetic and thermodynamic data is used to construct reaction profiles for these reactions. On the basis of the assumption that the transition state occurs on the way to formation of (η4-arene)Cr(CO)3(L) a linear correlation exists between the enthalpy of formation of the transition-state complex and changes in resonance energy of the fused arene ligands attributable to localization of the π bonds of the proposed η4 intermediate. The rate of binding of C6H6 to (THF)3Cr(CO)3 is 10% slower than for C6D6, implicating the importance of (η1-C6H6)Cr(CO)3(THF) 2 as an intermediate on the pathway to formation of (η6-C6H6)-Cr(CO)3.

Original languageEnglish
Pages (from-to)3692-3702
Number of pages11
JournalOrganometallics
Volume13
Issue number9
StatePublished - Dec 1 1994

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Carbon Monoxide
Electron transitions
Electron energy levels
Ground state
Ligands
Thiophenes
ligands
ground state
thiophenes
phenanthrene
energy
Toluene
pyrenes
anthracene
Benzene
naphthalene
toluene
Enthalpy
enthalpy
benzene

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Ground-state versus transition-state effects in arene displacement reactions of the complexes (η6-arene)Cr(CO)s : Linear dependence of transition-state energies and resonance energies of the arene ligands. / Zhang, Songshen; Shen, Jian Kun; Basolo, Fred; Ju, Telvin D.; Lang, Russell F.; Kiss, Gabor; Hoff, Carl.

In: Organometallics, Vol. 13, No. 9, 01.12.1994, p. 3692-3702.

Research output: Contribution to journalArticle

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abstract = "The rates of displacement of arene and thiophene ligands by P(n-Bu)3 in decalin and PPh3 in toluene have been studied. The reactions are first order in complex and incoming ligand. Rates of reaction increase in the order benzene < styrene < triphenylene < pyrene < phenanthrene < dimethylthiophene < naphthalene < thiophene < anthracene and span roughly 8 orders of magnitude. The thermodynamic stability of these species has also been investigated by solution calorimetry and equilibrium studies. The order of decreasing thermodynamic stability is benzene > dimethylthiophene > triphenylene > phenanthrene > thiophene > naphthalene > anthracene > pyrene and spans about 7 kcal/mol. The combination of kinetic and thermodynamic data is used to construct reaction profiles for these reactions. On the basis of the assumption that the transition state occurs on the way to formation of (η4-arene)Cr(CO)3(L) a linear correlation exists between the enthalpy of formation of the transition-state complex and changes in resonance energy of the fused arene ligands attributable to localization of the π bonds of the proposed η4 intermediate. The rate of binding of C6H6 to (THF)3Cr(CO)3 is 10{\%} slower than for C6D6, implicating the importance of (η1-C6H6)Cr(CO)3(THF) 2 as an intermediate on the pathway to formation of (η6-C6H6)-Cr(CO)3.",
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AB - The rates of displacement of arene and thiophene ligands by P(n-Bu)3 in decalin and PPh3 in toluene have been studied. The reactions are first order in complex and incoming ligand. Rates of reaction increase in the order benzene < styrene < triphenylene < pyrene < phenanthrene < dimethylthiophene < naphthalene < thiophene < anthracene and span roughly 8 orders of magnitude. The thermodynamic stability of these species has also been investigated by solution calorimetry and equilibrium studies. The order of decreasing thermodynamic stability is benzene > dimethylthiophene > triphenylene > phenanthrene > thiophene > naphthalene > anthracene > pyrene and spans about 7 kcal/mol. The combination of kinetic and thermodynamic data is used to construct reaction profiles for these reactions. On the basis of the assumption that the transition state occurs on the way to formation of (η4-arene)Cr(CO)3(L) a linear correlation exists between the enthalpy of formation of the transition-state complex and changes in resonance energy of the fused arene ligands attributable to localization of the π bonds of the proposed η4 intermediate. The rate of binding of C6H6 to (THF)3Cr(CO)3 is 10% slower than for C6D6, implicating the importance of (η1-C6H6)Cr(CO)3(THF) 2 as an intermediate on the pathway to formation of (η6-C6H6)-Cr(CO)3.

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