Dynamics of Photosubstitution Reactions of Fe(CO)5: An Ultrafast Infrared Study of High Spin Reactivity
Dynamics of Photosubstitution Reactions of Fe(CO)5: An Ultrafast Infrared Study of High Spin Reactivity
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Fe(CO)5 光取代反应动力学：高自旋反应性的超快红外研究
DOI：
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发表时间：
2001
期刊：
影响因子：
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通讯作者：
C. Harris
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文献类型：
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作者：
P. Snee;C. Payne;S. Mebane;K. Kotz;C. Harris
用飞秒紫外泵浦红外探针技术研究了Fe(CO)5与醇和三乙基膦在室温溶液中的光取代反应。Fe(CO)5在醇中的动力学表明，与三重态Fe(CO) 4相比，溶剂羟基的配位通常比单重态Fe(CO) 4的配位时间要快得多。这其中的物理原因是金属的碳氢键在三联体中要弱得多，因此可以快速重排到醇的羟基上。在三乙基膦光取代的情况下，反应分为平行通道，包括系统间交叉和自旋守恒的双羰基损失。使用密度泛函理论（DFT）和从头算量子化学计算对观察到的中间体进行了研究。
The photosubstitution reactions of Fe(CO)5 with alcohols and triethylphosphine have been studied in room temperature solution using femtosecond UV pump IR probe techniques. The dynamics of Fe(CO)5 in alcohols show that the coordination of the hydroxyl group of the solvent with triplet Fe(CO) 4 is generally much faster than the coordination timescale observed with comparable singlet species. The physical reason for this is the fact that the metal C-H agostic bond is much weaker for triplets, thus allowing fast rearrangement to the hydroxyl group of the alcohol. In the case of triethylphosphine photosubstitution, the reaction is divided into parallel channels which include intersystem crossing and a spin conserving double carbonyl loss. The intermediates observed were studied using density functional theory (DFT) as well as ab initio quantum chemical calculations.