Carbon Monoxide Insertion Reactions. I. The Carbonylation of Methyl Manganese Pentacarbonyl and Decarbonylation of Acetyl Manganese Pentacarbonyl
Carbon Monoxide Insertion Reactions. I. The Carbonylation of Methyl Manganese Pentacarbonyl and Decarbonylation of Acetyl Manganese Pentacarbonyl
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DOI：
10.1021/ic50001a008
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发表时间：
1962-01-01
影响因子：
4.6
通讯作者：
Cotton, F. Albert
中科院分区：
文献类型：
--
作者：
Calderazzo, Faust;Cotton, F. Albert
本文研究了常压下一氧化碳在不同溶剂和不同温度下CH_3Mn（CO）（5）+ CO = CH_2COMn（CO）（6）体系的平衡及正、逆反应速率。该反应在CH_3 Mn（CO）（3）和CO中均为一级反应，在常用溶剂（CH_3CH_2 OCH_2CH_2）（2）O中，得到以下数据：在30 ℃下平衡，K = 367 1.摩尔（-1），Δ H度= -12.6千卡。摩尔（-1），Δ F度= -3.55千卡。摩尔（-1），δ S度= -30.0卡摩尔（-1）度。（-1）。对于30 °的正向反应，k（1）= 8.99 × 10（-3）l。摩尔（-1）秒(-1)，Δ H* = 14.2 kcal。摩尔（-1），Δ F* = 20.6千卡。摩尔-1，Δ S* = -21.1卡摩尔（-1）度（-1）。对于30度下的逆反应，k（2）= 2.48 × 10（-5）秒。(-1)Δ H* 约为27千卡。摩尔（-1），Δ F* 约为24千卡。摩尔（-1），Δ S* 约为10.5卡摩尔（-1）度。（-1）。改变溶剂的效果似乎主要是在稳定一个有点极性的过渡态和特定的，分子溶剂的参与似乎是不重要的溶剂中使用的体介电常数的函数。可能的机制进行了讨论，涉及直接结合的CH 3 Mn（CO）（5）与CO被证明符合所有已知的事实，是优选的，虽然一个机制，涉及快速预平衡CH 3 Mn（CO）（6）= CH 3COMn（CO）（4）不能排除在这个阶段。
The equilibrium and the rates of the forward and reverse reactions in the system CH3Mn(CO)(5) + CO = CH2COMn(CO)(6) have been studied at atmospheric pressure of carbon monoxide in various solvents and at several temperatures. The reaction is first order in both CH3Mn(CO)(3) and CO. In (CH3CH2OCH2CH2)(2)O, the solvent most used, the following data have been obtained: For the equilibrium at 30 degrees, K = 367 1. mole(-1), Delta H degrees = -12.6 kcal. mole(-1), Delta F degrees = -3.55 kcal. mole(-1), Delta S degrees = -30.0 cal. mole(-1) deg.(-1). For the forward reaction at 30 degrees, k(1) = 8.99 X 10(-3) l. mole(-1) sec.(-1), Delta H* = 14.2 kcal. mole(-1), Delta F* = 20.6 kcal. mole-1, Delta S* = -21.1 cal. mole(-1) deg.(-1). For the reverse reaction at 30 degrees, k(2) = 2.48 X 10(-5) sec.(-1), Delta H* approximate to 27 kcal. mole(-1), Delta F* approximate to 24 kcal. mole(-1), Delta S* approximate to 10.5 cal. mole(-1) deg.(-1). The effect of changing the solvent appears to be mainly a function of the bulk dielectric constant in stabilizing a somewhat polar transition state and specific, molecular solvent participation does not appear to be important in the solvents used. Possible mechanisms are discussed and one involving direct combination of CH3Mn(CO)(5) with CO is shown to fit all the known facts and is preferred although a mechanism involving the rapid pre-equilibrium CH3Mn(CO)(6) = CH3COMn(CO)(4) cannot be ruled out at this stage.