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

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)367-372
Number of pages6
JournalJournal of the Chemical Society - Dalton Transactions
Issue number3
DOIs
Publication statusPublished - Feb 7 1999

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Cyclization
Ligands
Condensation
ethylenediamine
Oxygen
Geometry
Nitrogen
Iron
Metals
Binding Sites
Imidazolines
diethylenetriamine
Intermetallics
perchlorate

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

FeIIPbII and FeIII complexes of macrocyclic compartmental ligands : Different cyclization in stepwise template synthesis using FeII/PbII or FeIII/PbII pairs. / Furutachi, Hideki; Ishida, Akiko; Miyasaka, Hitoshi; Fukita, Nobuo; Ohba, Masaaki; Okawa, Hisashi; Koikawa, Masayuki.

In: Journal of the Chemical Society - Dalton Transactions, No. 3, 07.02.1999, p. 367-372.

Research output: Contribution to journalArticle

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abstract = "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) {\AA}. 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.",
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T1 - FeIIPbII and FeIII complexes of macrocyclic compartmental ligands

T2 - Different cyclization in stepwise template synthesis using FeII/PbII or FeIII/PbII pairs

AU - Furutachi, Hideki

AU - Ishida, Akiko

AU - Miyasaka, Hitoshi

AU - Fukita, Nobuo

AU - Ohba, Masaaki

AU - Okawa, Hisashi

AU - Koikawa, Masayuki

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N2 - 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.

AB - 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.

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