Selective Si-C Bond Cleavage on a Diorganosilicon Porphyrin Complex Bearing Different Axial Ligands
Selective Si-C Bond Cleavage on a Diorganosilicon Porphyrin Complex Bearing Different Axial Ligands
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DOI：
10.1246/cl.2009.362
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发表时间：
2009-04-05
影响因子：
1.6
通讯作者：
Kyushin, Soichiro
中科院分区：
文献类型：
--
作者：
Ishida, Shintaro;Yoshimura, Kimio;Kyushin, Soichiro
合成了四苯基卟啉甲基苯基硅配合物（简称Si（TPP）MePh），并对其结构进行了表征。虽然Si（TPP）MePh的Si-Ph键比Si-Me键长得多，但Si（TPP）MePh的光解和化学氧化选择性地裂解了Si-Me键，得到了新的苯基取代硅卟啉。对模型化合物的理论研究表明，显著的σ-π轨道相互作用提高了HOMO，并负责硅-碳键的断裂。苯基自由基对甲基自由基的不稳定性导致键的选择性断裂。
Tetraphenylporphyrinato methylphenylsilicon complex (abbreviated to Si(TPP)MePh) was synthesized and structurally characterized. Although the Si-Ph bond of Si(TPP)MePh is much longer than the Si-Me bond, photolysis and chemical oxidation of Si(TPP)MePh cleaved the Si-Me bond selectively and gave new phenyl-substituted silicon porphyrins. Theoretical studies of a model compound showed that significant sigma-pi orbital interaction raised the HOMO and is responsible for the silicon-carbon bond cleavage. The instability of phenyl radical to methyl radical caused selective bond cleavage.