Dinuclear CuII and NiII complexes of 3-formylsalicylic acid oxime

cis/trans topology and extension of a cis-CuII2 complex to a pentanuclear CuIICuIIMnIICuIICuII complex

K. Ikeda, Masaaki Ohba, H. Okawa

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Abstract

3-Formylsalicylic acid oxime (H3L) formed the following dinuclear CuII and NiII complexes: [Cu2(HL)2]·0.5H2O (1), Na[Cu2(HL)(L)]·3H2O (2) and [Ni2(HL)2]·2.5H2O (3). The structures of Na[Cu2(HL)(L)(H2O)] (2′) and [Ni2(HL)2(H2O)4]·8H 2O (3′) have been determined by X-ray crystallography. Complex 2 has a cis arrangement of the two ligands providing dissimilar {CuN2O2} and {CuO4} chromophores sharing the two phenolic oxygen atoms. The N2O2 cavity has a hydrogen-bonded N-O···H···O-N linkage as the lateral chain, and the Cu in this site has a square-pyramidal geometry with a water molecule at the axial site. The Cu in the O4 cavity has a planar geometry. Complex 3 has a trans configuration with respect to its two ligands and each Ni has a six-coordinate geometry with two water molecules at the axial sites. Complex 1 has a trans configuration based on its having a chemical formula and IR spectrum similar to 3. The following interconversion among dinuclear Cu complexes has been established by pH adjustment: trans-[Cu2(HL)2] (1) ⇌ cis-[Cu2(HL)(L)]- (2) ⇌ trans-[Cu2(L)2]2- (water molecules are omitted). On the other hand, 3 showed the following interconversion: trans-[Ni2(HL)2] (3) ⇌ trans-[Ni2(L)2]2-. The cis Cu2 complex 2 was reacted with MnII to afford [Mn{Cu2(HL)(L)}2(H2O)4]·H 2O·2DMF (4) that has a linear pentanuclear CuIICuIIMnIICuIICuII structure formed by the coordination of two molecules of 2 to a MnII through a carboxylate group.

Original languageEnglish
Pages (from-to)3119-3124
Number of pages6
JournalJournal of the Chemical Society, Dalton Transactions
Issue number20
Publication statusPublished - Nov 20 2001

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Oximes
Topology
Molecules
Geometry
Water
Ligands
X ray crystallography
Chromophores
Hydrogen
Oxygen
Atoms
3-formylsalicylic acid

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

@article{5b4185c44f4e4bd59dd4488793055743,
title = "Dinuclear CuII and NiII complexes of 3-formylsalicylic acid oxime: cis/trans topology and extension of a cis-CuII2 complex to a pentanuclear CuIICuIIMnIICuIICuII complex",
abstract = "3-Formylsalicylic acid oxime (H3L) formed the following dinuclear CuII and NiII complexes: [Cu2(HL)2]·0.5H2O (1), Na[Cu2(HL)(L)]·3H2O (2) and [Ni2(HL)2]·2.5H2O (3). The structures of Na[Cu2(HL)(L)(H2O)] (2′) and [Ni2(HL)2(H2O)4]·8H 2O (3′) have been determined by X-ray crystallography. Complex 2 has a cis arrangement of the two ligands providing dissimilar {CuN2O2} and {CuO4} chromophores sharing the two phenolic oxygen atoms. The N2O2 cavity has a hydrogen-bonded N-O···H···O-N linkage as the lateral chain, and the Cu in this site has a square-pyramidal geometry with a water molecule at the axial site. The Cu in the O4 cavity has a planar geometry. Complex 3 has a trans configuration with respect to its two ligands and each Ni has a six-coordinate geometry with two water molecules at the axial sites. Complex 1 has a trans configuration based on its having a chemical formula and IR spectrum similar to 3. The following interconversion among dinuclear Cu complexes has been established by pH adjustment: trans-[Cu2(HL)2] (1) ⇌ cis-[Cu2(HL)(L)]- (2) ⇌ trans-[Cu2(L)2]2- (water molecules are omitted). On the other hand, 3 showed the following interconversion: trans-[Ni2(HL)2] (3) ⇌ trans-[Ni2(L)2]2-. The cis Cu2 complex 2 was reacted with MnII to afford [Mn{Cu2(HL)(L)}2(H2O)4]·H 2O·2DMF (4) that has a linear pentanuclear CuIICuIIMnIICuIICuII structure formed by the coordination of two molecules of 2 to a MnII through a carboxylate group.",
author = "K. Ikeda and Masaaki Ohba and H. Okawa",
year = "2001",
month = "11",
day = "20",
language = "English",
pages = "3119--3124",
journal = "Dalton Transactions",
issn = "1470-479X",
publisher = "Royal Society of Chemistry",
number = "20",

}

TY - JOUR

T1 - Dinuclear CuII and NiII complexes of 3-formylsalicylic acid oxime

T2 - cis/trans topology and extension of a cis-CuII2 complex to a pentanuclear CuIICuIIMnIICuIICuII complex

AU - Ikeda, K.

AU - Ohba, Masaaki

AU - Okawa, H.

PY - 2001/11/20

Y1 - 2001/11/20

N2 - 3-Formylsalicylic acid oxime (H3L) formed the following dinuclear CuII and NiII complexes: [Cu2(HL)2]·0.5H2O (1), Na[Cu2(HL)(L)]·3H2O (2) and [Ni2(HL)2]·2.5H2O (3). The structures of Na[Cu2(HL)(L)(H2O)] (2′) and [Ni2(HL)2(H2O)4]·8H 2O (3′) have been determined by X-ray crystallography. Complex 2 has a cis arrangement of the two ligands providing dissimilar {CuN2O2} and {CuO4} chromophores sharing the two phenolic oxygen atoms. The N2O2 cavity has a hydrogen-bonded N-O···H···O-N linkage as the lateral chain, and the Cu in this site has a square-pyramidal geometry with a water molecule at the axial site. The Cu in the O4 cavity has a planar geometry. Complex 3 has a trans configuration with respect to its two ligands and each Ni has a six-coordinate geometry with two water molecules at the axial sites. Complex 1 has a trans configuration based on its having a chemical formula and IR spectrum similar to 3. The following interconversion among dinuclear Cu complexes has been established by pH adjustment: trans-[Cu2(HL)2] (1) ⇌ cis-[Cu2(HL)(L)]- (2) ⇌ trans-[Cu2(L)2]2- (water molecules are omitted). On the other hand, 3 showed the following interconversion: trans-[Ni2(HL)2] (3) ⇌ trans-[Ni2(L)2]2-. The cis Cu2 complex 2 was reacted with MnII to afford [Mn{Cu2(HL)(L)}2(H2O)4]·H 2O·2DMF (4) that has a linear pentanuclear CuIICuIIMnIICuIICuII structure formed by the coordination of two molecules of 2 to a MnII through a carboxylate group.

AB - 3-Formylsalicylic acid oxime (H3L) formed the following dinuclear CuII and NiII complexes: [Cu2(HL)2]·0.5H2O (1), Na[Cu2(HL)(L)]·3H2O (2) and [Ni2(HL)2]·2.5H2O (3). The structures of Na[Cu2(HL)(L)(H2O)] (2′) and [Ni2(HL)2(H2O)4]·8H 2O (3′) have been determined by X-ray crystallography. Complex 2 has a cis arrangement of the two ligands providing dissimilar {CuN2O2} and {CuO4} chromophores sharing the two phenolic oxygen atoms. The N2O2 cavity has a hydrogen-bonded N-O···H···O-N linkage as the lateral chain, and the Cu in this site has a square-pyramidal geometry with a water molecule at the axial site. The Cu in the O4 cavity has a planar geometry. Complex 3 has a trans configuration with respect to its two ligands and each Ni has a six-coordinate geometry with two water molecules at the axial sites. Complex 1 has a trans configuration based on its having a chemical formula and IR spectrum similar to 3. The following interconversion among dinuclear Cu complexes has been established by pH adjustment: trans-[Cu2(HL)2] (1) ⇌ cis-[Cu2(HL)(L)]- (2) ⇌ trans-[Cu2(L)2]2- (water molecules are omitted). On the other hand, 3 showed the following interconversion: trans-[Ni2(HL)2] (3) ⇌ trans-[Ni2(L)2]2-. The cis Cu2 complex 2 was reacted with MnII to afford [Mn{Cu2(HL)(L)}2(H2O)4]·H 2O·2DMF (4) that has a linear pentanuclear CuIICuIIMnIICuIICuII structure formed by the coordination of two molecules of 2 to a MnII through a carboxylate group.

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