Table 3. Rate Constants k (s–1) with Standard Deviations in Parentheses and Equilibrium Constant K at Different Temperatures for the Isomerization Reactions of [cis-MCl4(NO)(Hind)]− (M = Ru (1), Os (3)) and [trans-MCl4(NO)(Hind)]− (M = Ru (2), Os(4)) in C2D2Cl4.
| process | k(80 °C) × 10–6 | k(90 °C) × 10–6 | k(100 °C) × 10–6 | k(105 °C) × 10–6 | k(110 °C) × 10–6 | k(120 °C) × 10–6 | k(130 °C) × 10–6 | |
|---|---|---|---|---|---|---|---|---|
| [ cis-RuCl4(NO)(Hind)]− (1) | cis → trans | 0.58(8) | 1.78(2) | 5.51(6) | 8.3(1) | 20.1(7) | ||
| [trans-RuCl4(NO)(Hind)]− (2) | trans → cis | 1.05(6) | 2.66(3) | 12.2(1) | 19.5(2) | 50.1(5) | ||
| [RuCl4(NO)(Hind)]− | K = (kc–t)(kt–c) | 0.55 | 0.57 | 0.45 | 0.42 | 0.40 | ||
| cis-[OsCl4(NO)(Hind)]− (3) | cis → transa | 0.04(1) | 0.08(1) | 0.6(1) | 2.3(2) | |||
| trans-[OsCl4(NO)(Hind)]− (4) | trans → cis | 1.26(1) | 2.68(2) | 11.4(1) | 36.6(7) | |||
| [OsCl4(NO)(Hind)]− | K = (kc–t)(kt–c) | 0.03 | 0.03 | 0.05 | 0.06 |
a
The kinetic parameters were obtained from reversible first order law analysis of trans to cis conversion data of trans-[OsCl4(NO)(Hind)]− (4).