Abstract
The synthesis and properties of the actinide s-cis-diene/cis-2-butene-1,4-diyl complexes Cp′2U(η4-C4H6) (2), Cp′2Th(η4-C4H6) (3), and Cp′2Th(η4-CH2CMeCMeCH2) (4) (Cp′ = η5-CH3)5C5) are described. They can be readily prepared from Cp′2MCl2 (M = U, Th) and the appropriate (THF)2Mg(CH2CRCRCH2) reagent. Complex 2 but not 3 can also be prepared from the methane-eliminating reaction of Cp′2U(Me)Cl and 3-butenyl Grignard. The molecular structure of 3 has been determined by single-crystal X-ray diffraction. Cp′2Th(η4-C4H6) crystallizes in the monoclinic space group P21/c - C2h5 (no. 14) with four molecules in a unit cell of dimensions a = 9.236 (3) Å, b = 14.720 (4) Å, c = 17.437 (4) Å, and β = 105.48 (2)°. Least-squares refinement led to a value for the conventional R index (on F) of 0.049 for 2450 reflections having 2θMoKᾱ <50.7° and I > 3σ(I). The molecular structure consists of an unexceptional "bent sandwich" Cp′2Th fragment coordinated to an s-cis-η 4-butadiene ligand. The average Th-C distance to the terminal carbon atoms of the butadiene ligand, 2.57 (3, 3, 3, 2) Å, is only slightly less than that to the internal carbon atoms, 2.74 (3, 1, 1, 2) Å. The actinide butadiene complexes undergo inversion of the metallacyclopentene ring which is rapid on the NMR time scale at higher temperatures; ΔG≠, kcal mol-1 (Tc, K) = 17.0 ± 0.3 (394, 2), 15.0 ± 0.3 (299, 3), and 10.5 ± 0.3 (208, 4). Thermochemical studies of the thorium-butadiene bond disruption enthalpy in 3 and 4 using anaerobic batch-titration (t-BuOH) calorimetry indicate that the thorium-butadiene interaction enjoys no special stabilization. D(Th-butadiene) is comparable to that for relatively "weak" thorium-to-carbon σ bonds. No evidence for s-trans-butadiene coordination is found in any of the actinide butadiene complexes. While the actinide-butadiene linkage undergoes facile hydrogenolysis and protonolysis, the activation of C-H bonds on exogenous hydrocarbon molecules is not observed. The bond disruption enthalpy data indicate that such process are thermodynamically unfavorable.
| Original language | English |
|---|---|
| Pages (from-to) | 549-561 |
| Number of pages | 13 |
| Journal | Organometallics |
| Volume | 5 |
| Issue number | 3 |
| Publication status | Published - 1986 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry
Cite this
Actinide diene (2-Butene-1,4-diyl) complexes. Synthesis including a methyl-induced β-hydrogen elimination reaction, structures, structural dynamics, thermochemistry, and reactivity. / Smith, Gregory M.; Suzuki, Hiroharu; Sonnenberger, David C.; Day, Victor W.; Marks, Tobin J.
In: Organometallics, Vol. 5, No. 3, 1986, p. 549-561.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Actinide diene (2-Butene-1,4-diyl) complexes. Synthesis including a methyl-induced β-hydrogen elimination reaction, structures, structural dynamics, thermochemistry, and reactivity
AU - Smith, Gregory M.
AU - Suzuki, Hiroharu
AU - Sonnenberger, David C.
AU - Day, Victor W.
AU - Marks, Tobin J
PY - 1986
Y1 - 1986
N2 - The synthesis and properties of the actinide s-cis-diene/cis-2-butene-1,4-diyl complexes Cp′2U(η4-C4H6) (2), Cp′2Th(η4-C4H6) (3), and Cp′2Th(η4-CH2CMeCMeCH2) (4) (Cp′ = η5-CH3)5C5) are described. They can be readily prepared from Cp′2MCl2 (M = U, Th) and the appropriate (THF)2Mg(CH2CRCRCH2) reagent. Complex 2 but not 3 can also be prepared from the methane-eliminating reaction of Cp′2U(Me)Cl and 3-butenyl Grignard. The molecular structure of 3 has been determined by single-crystal X-ray diffraction. Cp′2Th(η4-C4H6) crystallizes in the monoclinic space group P21/c - C2h5 (no. 14) with four molecules in a unit cell of dimensions a = 9.236 (3) Å, b = 14.720 (4) Å, c = 17.437 (4) Å, and β = 105.48 (2)°. Least-squares refinement led to a value for the conventional R index (on F) of 0.049 for 2450 reflections having 2θMoKᾱ <50.7° and I > 3σ(I). The molecular structure consists of an unexceptional "bent sandwich" Cp′2Th fragment coordinated to an s-cis-η 4-butadiene ligand. The average Th-C distance to the terminal carbon atoms of the butadiene ligand, 2.57 (3, 3, 3, 2) Å, is only slightly less than that to the internal carbon atoms, 2.74 (3, 1, 1, 2) Å. The actinide butadiene complexes undergo inversion of the metallacyclopentene ring which is rapid on the NMR time scale at higher temperatures; ΔG≠, kcal mol-1 (Tc, K) = 17.0 ± 0.3 (394, 2), 15.0 ± 0.3 (299, 3), and 10.5 ± 0.3 (208, 4). Thermochemical studies of the thorium-butadiene bond disruption enthalpy in 3 and 4 using anaerobic batch-titration (t-BuOH) calorimetry indicate that the thorium-butadiene interaction enjoys no special stabilization. D(Th-butadiene) is comparable to that for relatively "weak" thorium-to-carbon σ bonds. No evidence for s-trans-butadiene coordination is found in any of the actinide butadiene complexes. While the actinide-butadiene linkage undergoes facile hydrogenolysis and protonolysis, the activation of C-H bonds on exogenous hydrocarbon molecules is not observed. The bond disruption enthalpy data indicate that such process are thermodynamically unfavorable.
AB - The synthesis and properties of the actinide s-cis-diene/cis-2-butene-1,4-diyl complexes Cp′2U(η4-C4H6) (2), Cp′2Th(η4-C4H6) (3), and Cp′2Th(η4-CH2CMeCMeCH2) (4) (Cp′ = η5-CH3)5C5) are described. They can be readily prepared from Cp′2MCl2 (M = U, Th) and the appropriate (THF)2Mg(CH2CRCRCH2) reagent. Complex 2 but not 3 can also be prepared from the methane-eliminating reaction of Cp′2U(Me)Cl and 3-butenyl Grignard. The molecular structure of 3 has been determined by single-crystal X-ray diffraction. Cp′2Th(η4-C4H6) crystallizes in the monoclinic space group P21/c - C2h5 (no. 14) with four molecules in a unit cell of dimensions a = 9.236 (3) Å, b = 14.720 (4) Å, c = 17.437 (4) Å, and β = 105.48 (2)°. Least-squares refinement led to a value for the conventional R index (on F) of 0.049 for 2450 reflections having 2θMoKᾱ <50.7° and I > 3σ(I). The molecular structure consists of an unexceptional "bent sandwich" Cp′2Th fragment coordinated to an s-cis-η 4-butadiene ligand. The average Th-C distance to the terminal carbon atoms of the butadiene ligand, 2.57 (3, 3, 3, 2) Å, is only slightly less than that to the internal carbon atoms, 2.74 (3, 1, 1, 2) Å. The actinide butadiene complexes undergo inversion of the metallacyclopentene ring which is rapid on the NMR time scale at higher temperatures; ΔG≠, kcal mol-1 (Tc, K) = 17.0 ± 0.3 (394, 2), 15.0 ± 0.3 (299, 3), and 10.5 ± 0.3 (208, 4). Thermochemical studies of the thorium-butadiene bond disruption enthalpy in 3 and 4 using anaerobic batch-titration (t-BuOH) calorimetry indicate that the thorium-butadiene interaction enjoys no special stabilization. D(Th-butadiene) is comparable to that for relatively "weak" thorium-to-carbon σ bonds. No evidence for s-trans-butadiene coordination is found in any of the actinide butadiene complexes. While the actinide-butadiene linkage undergoes facile hydrogenolysis and protonolysis, the activation of C-H bonds on exogenous hydrocarbon molecules is not observed. The bond disruption enthalpy data indicate that such process are thermodynamically unfavorable.
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M3 - Article
VL - 5
SP - 549
EP - 561
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 3
ER -