Pentalene: Formation, electronic, and vibrational structure
Pentalene: Formation, electronic, and vibrational structure
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DOI：
10.1021/ja963439t
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发表时间：
1997-02-26
影响因子：
15
通讯作者：
Zhu, ZD
中科院分区：
文献类型：
--
作者：
Bally, T;Chai, SY;Zhu, ZD
并环戊二烯（1）是第一次在氩气基质中通过光裂解相应的二聚体（2）。据发现，裂解发生在两个不同的步骤，其中第一个可能导致一个双自由基。1的特征在于它的电子和振动吸收光谱，其分配和解释参考不同的量子化学计算。这些表明，并环戊烯的前两个激发态涉及双激发构型，这在之前的电子结构讨论中被忽略了。由于并环戊二烯的反芳族性质，有利于具有局部单键和双键的C-2 h结构的π电子的扭曲力超过了将分子驱动为D-2 h结构的α电子的效应。
Pentalene (1) is generated for the first time in argon matrices by photocleavage of the corresponding dimer (2). It is found that the cleavage occurs in two distinct steps, the first of which leads presumably to a diradical. 1 is characterized by its electronic and vibrational absorption spectra which are assigned and interpreted with reference to different quantum chemical calculations. These show that the first two excited states of pentalene involve a doubly excited configuration which had been ignored in previous discussion of the electronic structure. Due to the antiaromatic nature of pentalene, the distortive force of the pi-electrons which favor a C-2h structure With localized single and double bonds predominates over the effect of the alpha-electrons which drive the molecule to a D-2h structure.