FeIIPbII and FeIII complexes of macrocyclic compartmental ligands: Different cyclization in stepwise template synthesis using FeII/PbII or FeIII/PbII pairs

Hideki Furutachi, Akiko Ishida, Hitoshi Miyasaka, Nobuo Fukita, Masaaki Ohba, Hisashi Okawa, Masayuki Koikawa

研究成果: ジャーナルへの寄稿記事

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The reaction of [bis(3-formyl-5-methylsalicylidene)ethylenediaminato]iron(II) with diethylenetriamine (dien) in the presence of PbII followed by the addition of NaNCS formed a FeIIPbII complex, [FePb(L1)(NCS)(dmf)(ClO4)] 1, where (L1)2- is a dinucleating macrocyclic compartmental ligand derived from the [2:1:1] condensation of 2,6-diformyl-4-methylphenol, ethylenediamine and dien, having "salen"- and "saldien"-like metal-binding sites sharing the phenolic entities. The Fe resides in the "salen" site and the Pb in the "saldien" site: the Fe⋯Pb intermetallic separation is 3.438(2) Å. The Fe assumes a square-pyramidal geometry with an isothiocyanate nitrogen at the apex. The Pb has a seven-coordinate geometry with a dmf oxygen and a perchlorate oxygen at the axial sites. Complex I reacts with molecular dioxygen to give a μ-oxo complex [{FePb(L1)(NCS)(dmf)(ClO4)}2(O)]. A similar reaction of chloro[bis(3-formyl-5-methylsalicylidene)ethylenediaminato]iron(III) with dien in the presence of PbII formed a mononuclear FeIII complex [Fe(H2L2)(NCS)][ClO4]2·dmf 2, where H2L2 is a macrocycle derived from the [2:2] condensation of 2,6-diformyl-4-methylphenol and dien. The Fe resides in one "saldien" site and assumes an octahedral geometry with an isothiocyanate nitrogen in one apical position. Another metal-binding site formed with dien shows unusual condensation; one primary amino group of the dien condenses with one formyl group to form an usual C=N linkage and the remaining primary and secondary amino groups of the dien condense with another formyl group to form a five-membered imidazoline ring.

元の言語英語
ページ(範囲)367-372
ページ数6
ジャーナルJournal of the Chemical Society - Dalton Transactions
発行部数3
DOI
出版物ステータス出版済み - 2 7 1999

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

フィンガープリント Fe<sup>II</sup>Pb<sup>II</sup> and Fe<sup>III</sup> complexes of macrocyclic compartmental ligands: Different cyclization in stepwise template synthesis using Fe<sup>II</sup>/Pb<sup>II</sup> or Fe<sup>III</sup>/Pb<sup>II</sup> pairs' の研究トピックを掘り下げます。これらはともに一意のフィンガープリントを構成します。

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