Template synthesis of macrocyclic dinuclear CuII complexes and conversion into mononuclear complexes by site-selective copper elimination

A. Hori, M. Yonemura, M. Ohba, H. Okawa

Research output: Contribution to journalArticle

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Abstract

The acyclic dinucleating ligand, N,N′-dimethyl-N,N′-trimethylenedi-(3-formyl-2-hydroxy-5- methylbenzylamine) (H2L), has been prepared. It combines two CuII ions with its N(amine)2O2 and O4 metal-binding sites to form a dinuclear complex [Cu2(L)](ClO4)2. The [1:1] condensation of [Cu2(L)](ClO4)2 with an aliphatic or aromatic diamine has provided macrocyclic dinuclear CuII complexes [Cu2(Li)](ClO4)2 (Li = L1 for the diamine = ethylenediamine, L2 for trimethylenediamine, L3 for tetramethylenediamine, L4 for o-phenylenediamine and L5 for 1,8-diaminonaphthalene). X-ray crystallographic studies for [Cu2(L1)(H2O)](ClO4) 2MeCN and [Cu2(L5)](ClO4)22MeOH demonstrate a macrocyclic dinuclear core structure with the two CuII ions in the N(amine)2O2 and N(imine)2O2 sites, in the Cu-Cu separation of ca. 3.0 Å. The dinuclear complexes are studied in magnetic, electronic spectral and electrochemical properties. The treatment of the dinuclear complexes with Na2S in acetonitrile resulted in the elimination of one Cu to afford the mononuclear complexes [Cu(Li)]xNaClO4. The X-ray crystallography for [Cu(L2)], [Cu(L3)NaClO4 and [Cu(L4)] has demonstrated that the Cu in the N(amine)2O2 site is selectively eliminated. In the latter complex, the Na1ion is accommodated in the aminic site.

Original languageEnglish
Pages (from-to)495-503
Number of pages9
JournalBulletin of the Chemical Society of Japan
Volume74
Issue number3
DOIs
Publication statusPublished - 2001 Mar 1
Externally publishedYes

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Copper
Amines
ethylenediamine
Diamines
Ions
Imines
Putrescine
X ray crystallography
Electrochemical properties
Condensation
Metals
Binding Sites
perchlorate
Ligands
X rays

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Template synthesis of macrocyclic dinuclear CuII complexes and conversion into mononuclear complexes by site-selective copper elimination. / Hori, A.; Yonemura, M.; Ohba, M.; Okawa, H.

In: Bulletin of the Chemical Society of Japan, Vol. 74, No. 3, 01.03.2001, p. 495-503.

Research output: Contribution to journalArticle

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abstract = "The acyclic dinucleating ligand, N,N′-dimethyl-N,N′-trimethylenedi-(3-formyl-2-hydroxy-5- methylbenzylamine) (H2L), has been prepared. It combines two CuII ions with its N(amine)2O2 and O4 metal-binding sites to form a dinuclear complex [Cu2(L)](ClO4)2. The [1:1] condensation of [Cu2(L)](ClO4)2 with an aliphatic or aromatic diamine has provided macrocyclic dinuclear CuII complexes [Cu2(Li)](ClO4)2 (Li = L1 for the diamine = ethylenediamine, L2 for trimethylenediamine, L3 for tetramethylenediamine, L4 for o-phenylenediamine and L5 for 1,8-diaminonaphthalene). X-ray crystallographic studies for [Cu2(L1)(H2O)](ClO4) 2MeCN and [Cu2(L5)](ClO4)22MeOH demonstrate a macrocyclic dinuclear core structure with the two CuII ions in the N(amine)2O2 and N(imine)2O2 sites, in the Cu-Cu separation of ca. 3.0 {\AA}. The dinuclear complexes are studied in magnetic, electronic spectral and electrochemical properties. The treatment of the dinuclear complexes with Na2S in acetonitrile resulted in the elimination of one Cu to afford the mononuclear complexes [Cu(Li)]xNaClO4. The X-ray crystallography for [Cu(L2)], [Cu(L3)NaClO4 and [Cu(L4)] has demonstrated that the Cu in the N(amine)2O2 site is selectively eliminated. In the latter complex, the Na1ion is accommodated in the aminic site.",
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N2 - The acyclic dinucleating ligand, N,N′-dimethyl-N,N′-trimethylenedi-(3-formyl-2-hydroxy-5- methylbenzylamine) (H2L), has been prepared. It combines two CuII ions with its N(amine)2O2 and O4 metal-binding sites to form a dinuclear complex [Cu2(L)](ClO4)2. The [1:1] condensation of [Cu2(L)](ClO4)2 with an aliphatic or aromatic diamine has provided macrocyclic dinuclear CuII complexes [Cu2(Li)](ClO4)2 (Li = L1 for the diamine = ethylenediamine, L2 for trimethylenediamine, L3 for tetramethylenediamine, L4 for o-phenylenediamine and L5 for 1,8-diaminonaphthalene). X-ray crystallographic studies for [Cu2(L1)(H2O)](ClO4) 2MeCN and [Cu2(L5)](ClO4)22MeOH demonstrate a macrocyclic dinuclear core structure with the two CuII ions in the N(amine)2O2 and N(imine)2O2 sites, in the Cu-Cu separation of ca. 3.0 Å. The dinuclear complexes are studied in magnetic, electronic spectral and electrochemical properties. The treatment of the dinuclear complexes with Na2S in acetonitrile resulted in the elimination of one Cu to afford the mononuclear complexes [Cu(Li)]xNaClO4. The X-ray crystallography for [Cu(L2)], [Cu(L3)NaClO4 and [Cu(L4)] has demonstrated that the Cu in the N(amine)2O2 site is selectively eliminated. In the latter complex, the Na1ion is accommodated in the aminic site.

AB - The acyclic dinucleating ligand, N,N′-dimethyl-N,N′-trimethylenedi-(3-formyl-2-hydroxy-5- methylbenzylamine) (H2L), has been prepared. It combines two CuII ions with its N(amine)2O2 and O4 metal-binding sites to form a dinuclear complex [Cu2(L)](ClO4)2. The [1:1] condensation of [Cu2(L)](ClO4)2 with an aliphatic or aromatic diamine has provided macrocyclic dinuclear CuII complexes [Cu2(Li)](ClO4)2 (Li = L1 for the diamine = ethylenediamine, L2 for trimethylenediamine, L3 for tetramethylenediamine, L4 for o-phenylenediamine and L5 for 1,8-diaminonaphthalene). X-ray crystallographic studies for [Cu2(L1)(H2O)](ClO4) 2MeCN and [Cu2(L5)](ClO4)22MeOH demonstrate a macrocyclic dinuclear core structure with the two CuII ions in the N(amine)2O2 and N(imine)2O2 sites, in the Cu-Cu separation of ca. 3.0 Å. The dinuclear complexes are studied in magnetic, electronic spectral and electrochemical properties. The treatment of the dinuclear complexes with Na2S in acetonitrile resulted in the elimination of one Cu to afford the mononuclear complexes [Cu(Li)]xNaClO4. The X-ray crystallography for [Cu(L2)], [Cu(L3)NaClO4 and [Cu(L4)] has demonstrated that the Cu in the N(amine)2O2 site is selectively eliminated. In the latter complex, the Na1ion is accommodated in the aminic site.

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