Synthesis of pure iron(II) mesotetraphenylchlorin complexes via a versatile general method of iron insertion into chlorins

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• 作者：Marwan Kobeissi^a ; ^{marwan.kobeissi@liu.edu.lb} ; Khalil Cherry^a ; Mahmoud K. Faraj^b ; ^{mahmoud.faraj@liu.edu.lb} ; Gé ; rard Simonneaux^c ; ^{gerard.simonneaux@univ-rennes1.fr}
• 关键词：Iron chlorins ; Phosphines ; Isocyanides ; Diamagnetic complexes ; Transmetallation ; Cadmium
• 刊名：Inorganica Chimica Acta
• 出版年：2013
• 出版时间：24 February, 2013
• 年：2013
• 卷：396
• 期：Complete
• 页码：30-34
• 全文大小：442 K

文摘

An original synthesis of pure (tetraphenylchlorinato)iron(III) chloride (1) is reported. Insertion of iron is achieved using 1.2 equivalents of cadmium acetate in DMF at 110 ¡ãC, followed by a transmetallation reaction (in situ) using 8 equivalents of iron(II) chloride tetrahydrate in acetone at 60 ¡ãC. The ¹H NMR shifts at 25 ¡ãC of the pyrrole protons varied from 60 to 100 ppm. The absence of the signal at 80 ppm related to undesired (tetraphenylporphirinato)iron(III) chloride is a purity criterion and shows the importance of the method used.

Reaction of (tetraphenylchlorinato)iron(III) chloride (1) with four equivalents of tert-butyl isocyanide, 2,6-xylyl isocyanide and dimethylphenylphosphine in the presence of zinc amalgam in dichloromethane (DCM) afforded pure Fe^II(TPC)(t-BuNC)₂ (2), Fe^II(TPC)(2,6-xylylNC)₂ (3) and Fe^II(TPC)[P(Me)₂Ph]₂ (4) respectively.