Theoretical study on the phenyl torsional potentials of trans-diphenyldiphosphene.
Theoretical study on the phenyl torsional potentials of trans-diphenyldiphosphene.
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DOI：
10.1021/jp8043972
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发表时间：
2008-08
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影响因子：
--
通讯作者：
Yoshiaki Amatatsu
中科院分区：
文献类型：
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作者：
Yoshiaki Amatatsu
用从头算完全活性空间自洽场（CASSCF）方法研究了反式偶氮苯（t-AZB）的类似物反式二苯基二膦（t-DPP）的苯基扭转势.虽然t-DPP和t-AZB的电子结构相似，但它们的苯基扭转势不同。在S 0中，t-DPP的势能曲线在C2和Ci对称的非平面构象处有双重极小值，而t-AZB的势能曲线仅在C2 h对称的平面构象处有极小值.在S1中，t-AZB的苯基扭转比在S 0中受到更多的平面几何阻碍。另一方面，t-DPP的苯基扭转被促进，使得苯基基团在Franck-Condon区域周围垂直扭转于PP双键。评论的实验结果，现实的dipophenes保护的庞大的取代基也作出。
The phenyl torsional potentials of trans-diphenyldiphosphene ( trans-phosphobenzene; t-DPP), which is an analogue of trans-azobenzene ( t-AZB), have been examined by means of ab initio complete active space self-consistent field (CASSCF) calculations. Though the electronic structures of t-DPP are similar to those of t-AZB, the phenyl torsional potentials are different from each other. In S 0, the potential energy curve of t-DPP has double minima at nonplanar conformations with C 2 and C i symmetries, while that of t-AZB has only minimum at a planar conformation with C 2 h . In S 1, the phenyl torsion of t-AZB is impeded from a planar geometry more than that in S 0. On the other hand, the phenyl torsion of t-DPP is promoted so that the phenyl groups are perpendicularly twisted against the PP double bond around the Franck-Condon region. Comments on the experimental findings of realistic diphosphenes protected by bulky substituents are also made.