金属ポルフィリン錯体の光反応　　中心金属‐軸配位子結合の光活性化

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  • Photochemical Activation of Metal-Carbon Bond in Zinc and Aluminium Porphyrins
  • キンゾク ポルフィリン サクタイ ノ ヒカリ ハンノウ チュウシン キンゾク

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Irradiation with visible light (>420nm) has induced a remarkable effect on the reactivity of the metal-carbon bond in metalloporphyrins such as ethyl(N-methyltetraphenylporphinato)zinc (NMTPPZnEt) and ethyl(tetraphenylporphinato)aluminium (TPPAlEt) which have an alkyl group bound to the metal via c bond as an axial ligand. NMTPPZnEt underwent the homolytic cleavage of the ethyl-zinc group in dichloromethane resulting in the substitution of a chlorine for an ethyl group. In dibromomethane or diiodomethane the reaction proceeded more rapidly, while in benzene the homolysis proceeded only with difficulty. Irradiation of visible light also showed a dramatic effect on the reactivity of NMTPPZnEt and TPPAlEt in the substitution reaction with, hindered phenols such as 2, 6-di-t-butyl-4-methylphenol, to form the metalloporphyrins with the corresponding phenoxyl group bound to the central metal atom. The reactivity of the ethyl group bound to the central metal atom is considered to be increased via photoexcitation of the porphyrin moiety.

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