Theoretical study of the gas-phase Fe(CO)5 catalyzed water gas shift reaction:: A new mechanism proposed
Theoretical study of the gas-phase Fe(CO)5 catalyzed water gas shift reaction:: A new mechanism proposed
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DOI：
10.1021/ic049159t
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发表时间：
2004-12-27
影响因子：
4.6
通讯作者：
Barrows, SE
中科院分区：
文献类型：
--
作者：
Barrows, SE
研究了气相 Fe(CO)(5) 和碱催化水煤气变换反应的新机制。此处描述的反应途径预计在 B3LYP/6-31++G(d,p) 水平上与经典机制具有积极竞争性。这里探索的反应路径涉及能量无垒形成 (CO)(4)FeCOOH-（系统的催化剂），通过添加 CO 诱导脱羧得到 (CO)(4)FeCHO，以及在 (CO)(4)FeCHO 中间体中添加 H2O 时放出 H-2。使用 B3LYP 方法预测最后两步的能量势垒分别为 21.2 和 42.0 kcal/mol。
A novel mechanism for the gas-phase Fe(CO)(5) and base catalyzed water gas shift reaction has been examined. The reaction pathway described here is predicted at the B3LYP/6-31++G(d,p) level to be energetically competitive with the classic mechanism. The reaction path explored here involves the energetically barrierless formation of (CO)(4)FeCOOH- (the catalyst of the system) decarboxylation induced by the addition of CO to give (CO)(4)FeCHO, and evolution of H-2 upon addition of H2O to the (CO)(4)FeCHO intermediate. The energetic barriers predicted for the last two steps are 21.2 and 42.0 kcal/mol, respectively, using the B3LYP method.