Intrinsic barriers to atom transfer: Self-exchange reactions of CpM(CO)3X/CpM(CO)3 - halide couples

Carolyn L. Schwarz, R Morris Bullock, Carol Creutz

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Abstract

Rate constants and activation parameters were measured for the self-exchange of CpM(CO)3 - with CpM(CO)3X in CD3CN solvent: CpM(CO)3 - + CpM(CO)3X ⇌CpM(CO)3X + CpM(CO)3 - The self-exchange reactions were followed by 1H NMR spectroscopy: For the X = I complexes, standard line width measurements yield (M = Mo) k(298) = 1.5 × 104 M-1 s-1 (ΔH = 6.4 (±0.4) kcal mol-1, ΔS = -18 (±1.5) cal K-1 mo-1) and (M = W) k(298) = 4.5 × 103 M-1 s-1 (ΔH = 7.5 (±0.1) kcal mol-1, ΔS = -16.8 (±0.5) cal K-1 mol-1). For the X = Br complexes, magnetization-transfer experiments yield (M = Mo) k(298) = 1.6 × 101 M-1 S-1 (ΔH = 12.1 (±4.5) kcal mol-1, ΔS = -12 (±15) cal K-1 mol-1) and (M = W) k(298) = 1.5 M-1 S-1 (ΔH = 15.1 (±5.2) kcal mol-1, ΔS = -7 (±16) cal K-1 mol-1); 1H NMR longitudinal relaxation times T1 for the Cp groups of the reactants are typically 40 s. The X = Cl systems were studied by conventional techniques, with the rates of "transfer" of Cp-d5 from (Cp-D5)W(CO)3 - to CpW(CO)3Cl being monitored; for M = Mo, k(298) = 9.0 × 10-2 M-1 s-1 (ΔH‡ = 18.9 (±1.0) kcal mol-1, ΔS = 0 (±4) cal K-1 mol-1) and for M = W, k(298) = 2.1 × 10-3 M-1 s-1 (ΔH = 17.7 (±3.3) kcal mol-1, ΔS = -11 (±11) cal K-1 mol-1). For X = CH3, the CpW-(CO)3-/CpW(CO)3CH3 self-exchange rate constant, also determined by monitoring rates of "transfer" of Cp-d5 from (Cp-d5)W(CO)3 - to CpW(CO)3X, is ≈ 1 × 10-5 M-1 s-1 at 335 K. The latter self-exchange reaction is discussed in terms of the intrinsic barrier for oxidative addition to the anion. For the X = halogen exchanges, the role of the M(I) ("metal radical") state is considered, and it is concluded that the latter isovalent state is not an intermediate for these systems. However, the isovalent state may serve to stabilize the transition state for two-electron transfer between the metal centers through configuration interaction. Our results, taken with those for other X = halogen systems, indicate that effective transfer of X+ may be intrinsically rapid when both reactants are 18-electron species and steric factors are favorable.

Original languageEnglish
Pages (from-to)1225-1236
Number of pages12
JournalJournal of the American Chemical Society
Volume113
Issue number4
Publication statusPublished - Feb 13 1991

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Carbon Monoxide
Rate constants
Ion exchange
Atoms
Electrons
Electron transitions
Metals
Linewidth
Relaxation time
Nuclear magnetic resonance spectroscopy
Magnetization
Negative ions
Chemical activation
Nuclear magnetic resonance
Monitoring
Halogens
Experiments
Anions
Magnetic Resonance Spectroscopy

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Intrinsic barriers to atom transfer : Self-exchange reactions of CpM(CO)3X/CpM(CO)3 - halide couples. / Schwarz, Carolyn L.; Bullock, R Morris; Creutz, Carol.

In: Journal of the American Chemical Society, Vol. 113, No. 4, 13.02.1991, p. 1225-1236.

Research output: Contribution to journalArticle

@article{54bfa7b6ae0342d0ade5967175add41a,
title = "Intrinsic barriers to atom transfer: Self-exchange reactions of CpM(CO)3X/CpM(CO)3 - halide couples",
abstract = "Rate constants and activation parameters were measured for the self-exchange of CpM(CO)3 - with CpM(CO)3X in CD3CN solvent: CpM(CO)3 - + CpM(CO)3X ⇌CpM(CO)3X + CpM(CO)3 - The self-exchange reactions were followed by 1H NMR spectroscopy: For the X = I complexes, standard line width measurements yield (M = Mo) k(298) = 1.5 × 104 M-1 s-1 (ΔH‡ = 6.4 (±0.4) kcal mol-1, ΔS‡ = -18 (±1.5) cal K-1 mo-1) and (M = W) k(298) = 4.5 × 103 M-1 s-1 (ΔH‡ = 7.5 (±0.1) kcal mol-1, ΔS‡ = -16.8 (±0.5) cal K-1 mol-1). For the X = Br complexes, magnetization-transfer experiments yield (M = Mo) k(298) = 1.6 × 101 M-1 S-1 (ΔH‡ = 12.1 (±4.5) kcal mol-1, ΔS‡ = -12 (±15) cal K-1 mol-1) and (M = W) k(298) = 1.5 M-1 S-1 (ΔH‡ = 15.1 (±5.2) kcal mol-1, ΔS‡ = -7 (±16) cal K-1 mol-1); 1H NMR longitudinal relaxation times T1 for the Cp groups of the reactants are typically 40 s. The X = Cl systems were studied by conventional techniques, with the rates of {"}transfer{"} of Cp-d5 from (Cp-D5)W(CO)3 - to CpW(CO)3Cl being monitored; for M = Mo, k(298) = 9.0 × 10-2 M-1 s-1 (ΔH‡ = 18.9 (±1.0) kcal mol-1, ΔS‡ = 0 (±4) cal K-1 mol-1) and for M = W, k(298) = 2.1 × 10-3 M-1 s-1 (ΔH‡ = 17.7 (±3.3) kcal mol-1, ΔS‡ = -11 (±11) cal K-1 mol-1). For X = CH3, the CpW-(CO)3-/CpW(CO)3CH3 self-exchange rate constant, also determined by monitoring rates of {"}transfer{"} of Cp-d5 from (Cp-d5)W(CO)3 - to CpW(CO)3X, is ≈ 1 × 10-5 M-1 s-1 at 335 K. The latter self-exchange reaction is discussed in terms of the intrinsic barrier for oxidative addition to the anion. For the X = halogen exchanges, the role of the M(I) ({"}metal radical{"}) state is considered, and it is concluded that the latter isovalent state is not an intermediate for these systems. However, the isovalent state may serve to stabilize the transition state for two-electron transfer between the metal centers through configuration interaction. Our results, taken with those for other X = halogen systems, indicate that effective transfer of X+ may be intrinsically rapid when both reactants are 18-electron species and steric factors are favorable.",
author = "Schwarz, {Carolyn L.} and Bullock, {R Morris} and Carol Creutz",
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T2 - Self-exchange reactions of CpM(CO)3X/CpM(CO)3 - halide couples

AU - Schwarz, Carolyn L.

AU - Bullock, R Morris

AU - Creutz, Carol

PY - 1991/2/13

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N2 - Rate constants and activation parameters were measured for the self-exchange of CpM(CO)3 - with CpM(CO)3X in CD3CN solvent: CpM(CO)3 - + CpM(CO)3X ⇌CpM(CO)3X + CpM(CO)3 - The self-exchange reactions were followed by 1H NMR spectroscopy: For the X = I complexes, standard line width measurements yield (M = Mo) k(298) = 1.5 × 104 M-1 s-1 (ΔH‡ = 6.4 (±0.4) kcal mol-1, ΔS‡ = -18 (±1.5) cal K-1 mo-1) and (M = W) k(298) = 4.5 × 103 M-1 s-1 (ΔH‡ = 7.5 (±0.1) kcal mol-1, ΔS‡ = -16.8 (±0.5) cal K-1 mol-1). For the X = Br complexes, magnetization-transfer experiments yield (M = Mo) k(298) = 1.6 × 101 M-1 S-1 (ΔH‡ = 12.1 (±4.5) kcal mol-1, ΔS‡ = -12 (±15) cal K-1 mol-1) and (M = W) k(298) = 1.5 M-1 S-1 (ΔH‡ = 15.1 (±5.2) kcal mol-1, ΔS‡ = -7 (±16) cal K-1 mol-1); 1H NMR longitudinal relaxation times T1 for the Cp groups of the reactants are typically 40 s. The X = Cl systems were studied by conventional techniques, with the rates of "transfer" of Cp-d5 from (Cp-D5)W(CO)3 - to CpW(CO)3Cl being monitored; for M = Mo, k(298) = 9.0 × 10-2 M-1 s-1 (ΔH‡ = 18.9 (±1.0) kcal mol-1, ΔS‡ = 0 (±4) cal K-1 mol-1) and for M = W, k(298) = 2.1 × 10-3 M-1 s-1 (ΔH‡ = 17.7 (±3.3) kcal mol-1, ΔS‡ = -11 (±11) cal K-1 mol-1). For X = CH3, the CpW-(CO)3-/CpW(CO)3CH3 self-exchange rate constant, also determined by monitoring rates of "transfer" of Cp-d5 from (Cp-d5)W(CO)3 - to CpW(CO)3X, is ≈ 1 × 10-5 M-1 s-1 at 335 K. The latter self-exchange reaction is discussed in terms of the intrinsic barrier for oxidative addition to the anion. For the X = halogen exchanges, the role of the M(I) ("metal radical") state is considered, and it is concluded that the latter isovalent state is not an intermediate for these systems. However, the isovalent state may serve to stabilize the transition state for two-electron transfer between the metal centers through configuration interaction. Our results, taken with those for other X = halogen systems, indicate that effective transfer of X+ may be intrinsically rapid when both reactants are 18-electron species and steric factors are favorable.

AB - Rate constants and activation parameters were measured for the self-exchange of CpM(CO)3 - with CpM(CO)3X in CD3CN solvent: CpM(CO)3 - + CpM(CO)3X ⇌CpM(CO)3X + CpM(CO)3 - The self-exchange reactions were followed by 1H NMR spectroscopy: For the X = I complexes, standard line width measurements yield (M = Mo) k(298) = 1.5 × 104 M-1 s-1 (ΔH‡ = 6.4 (±0.4) kcal mol-1, ΔS‡ = -18 (±1.5) cal K-1 mo-1) and (M = W) k(298) = 4.5 × 103 M-1 s-1 (ΔH‡ = 7.5 (±0.1) kcal mol-1, ΔS‡ = -16.8 (±0.5) cal K-1 mol-1). For the X = Br complexes, magnetization-transfer experiments yield (M = Mo) k(298) = 1.6 × 101 M-1 S-1 (ΔH‡ = 12.1 (±4.5) kcal mol-1, ΔS‡ = -12 (±15) cal K-1 mol-1) and (M = W) k(298) = 1.5 M-1 S-1 (ΔH‡ = 15.1 (±5.2) kcal mol-1, ΔS‡ = -7 (±16) cal K-1 mol-1); 1H NMR longitudinal relaxation times T1 for the Cp groups of the reactants are typically 40 s. The X = Cl systems were studied by conventional techniques, with the rates of "transfer" of Cp-d5 from (Cp-D5)W(CO)3 - to CpW(CO)3Cl being monitored; for M = Mo, k(298) = 9.0 × 10-2 M-1 s-1 (ΔH‡ = 18.9 (±1.0) kcal mol-1, ΔS‡ = 0 (±4) cal K-1 mol-1) and for M = W, k(298) = 2.1 × 10-3 M-1 s-1 (ΔH‡ = 17.7 (±3.3) kcal mol-1, ΔS‡ = -11 (±11) cal K-1 mol-1). For X = CH3, the CpW-(CO)3-/CpW(CO)3CH3 self-exchange rate constant, also determined by monitoring rates of "transfer" of Cp-d5 from (Cp-d5)W(CO)3 - to CpW(CO)3X, is ≈ 1 × 10-5 M-1 s-1 at 335 K. The latter self-exchange reaction is discussed in terms of the intrinsic barrier for oxidative addition to the anion. For the X = halogen exchanges, the role of the M(I) ("metal radical") state is considered, and it is concluded that the latter isovalent state is not an intermediate for these systems. However, the isovalent state may serve to stabilize the transition state for two-electron transfer between the metal centers through configuration interaction. Our results, taken with those for other X = halogen systems, indicate that effective transfer of X+ may be intrinsically rapid when both reactants are 18-electron species and steric factors are favorable.

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