| Autor: |
Paw, Witold, Bower, David, Bierdeman, David, Keister, Jerome, Schulman, Edward |
| Zdroj: |
Journal of Coordination Chemistry; November 1996, Vol. 39 Issue: 3 p199-210, 12p |
| Abstrakt: |
The kinetics for isomerization of HRu3 (μ3-η3-EtSCCMeCMe)(CO)9 TO Ru3(μ-SEt) (μ3-η3-CCMeCHMe)(CO)9, were determined. The overall process involves C-H elimination, C-S and Ru-Ru bond cleavage and Ru2(μ-S) bond formation. Activation parameters were determined from the temperature dependence (ΔH‡ = 127(3) kJ/mol, ΔS‡= 56(11) J/mol-K) and from the pressure dependence (0-207 MPa, ΔV‡0 +12.7(1.1) cm3/mol, Δβ‡ = +0.037(0.012) cm3/(mol-MPa)) of the rate constant. The data are consistent with an intramolecular reaction involving significant metal-metal or carbon-sulfur bond cleavage in the transition state. The activation volume is too large to be accommodated by C-H elimination alone and CO dissociation is not involved. |
| Databáze: |
Supplemental Index |
| Externí odkaz: |
|
