Coordination-position isomeric MIICuIIand CuIIMII (M = Co, Ni, Zn) complexes derived from macrocyclic compartmental ligands

Masami Yonemura; Keisuke Arimura; Koji Inoue; Naoki Usuki; Masaaki Ohba; Hisashi Okawa

doi:10.1021/ic010499d

Coordination-position isomeric M^IICu^IIand Cu^IIM^II (M = Co, Ni, Zn) complexes derived from macrocyclic compartmental ligands

Masami Yonemura
, Keisuke Arimura
, Koji Inoue
, Naoki Usuki
, Masaaki Ohba
, Hisashi Okawa

無機・分析化学

研究成果: ジャーナルへの寄稿 › 学術誌 › 査読

53 被引用数 (Scopus)

抄録

The dinucleating macrocydic ligands (L^2;2)^2- and (L^2;3)^2-, comprised of two 2-[(N-methylamino)methyl]-6-(iminomethyl)-4-bromophenolate entities combined by the -(CH₂)₂- chain between the two aminic nitrogen atoms and by the -(CH₂)₂- or -(CH₂)₃- chain between the two iminic nitrogen atoms, have afforded the following M^IICu^II complexes: [CoCu(L^2;2)](ClO₄)₂·MeCN (1A), [NiCu(L^2;2)](ClO₄)₂ (2A), [ZnCu(L^2;2)](ClO₄)₂·0.5MeCN· EtOH (3A), [CoCu(L^2;3)(MeCN)·(2-PrOH)](ClO₄)₂ (4A), [NiCu(L^2;3)](ClO₄)₂ (5A), and [ZnCu(L^2;3)](ClO₄)₂·1.5DMF (6A). [CoCu(L^2;2)(MeCN)₃](ClO₄)₂ (1A′) crystallizes in the monoclinic space group P2₁/n, a = 11.691(2) Å, b = 18.572(3) Å, c = 17.058(3) Å, β = 91.18(2)°, V = 3703(1) Å³, and Z = 4. [NiCu(L^2;2)(DMF)₂](ClO₄)₂ (2A′) crystallizes in the triclinic space group P1̄, a = 11.260(2) Å, b = 16.359(6) Å, c = 10.853(4) Å, α = 96.98(3)°, β = 91.18(2)°, γ = 75.20(2)°, V = 1917(1) Å³, and Z = 2. 4A crystallizes in the monoclinic space group P2₁/c₁, a = 15.064(8) Å, b = 11.434(5) Å, c = 21.352(5) Å, β = 95.83(2)°, V = 3659(2) Å³, and Z = 4. The X-ray crystallographic results demonstrate the M^II to reside in the N(amine)₂O₂ site and the Cu^II in the N(imine)₂O₂ site. The complexes 1-6 are regarded to be isomeric with [CuCo(L^2;2))](ClO₄)₂·DMF (1B), [CuNi(L^2;2))](ClO₄)₂·DMF·MeOH (2B), [CuZn(L^2;2))](ClO₄)₂·H₂O (3B)), [CuCo(L^2;3))](ClO₄)₂·2H₂O (4B), [CuNi(L^2;3))](ClO₄)₂ (5B), and [CuZn(L^2;3))](ClO₄)₂·H₂O (6B) reported previously, when we ignore exogenous donating and solvating molecules. The isomeric M^IICu^II and Cu^IIM^II complexes are differentiated by X-ray structural, magnetic, visible spectroscopic, and electrochemical studies. The two isomeric forms are significantly stabilized by the "macrocyclic effect" of the ligands, but 1A is converted into 1B on an electrode, and 2A is converted into 2B at elevated temperature.

本文言語	英語
ページ（範囲）	582-589
ページ数	8
ジャーナル	Inorganic chemistry
巻	41
号	3
DOI	https://doi.org/10.1021/ic010499d
出版ステータス	出版済み - 2月 11 2002

!!!All Science Journal Classification (ASJC) codes

物理化学および理論化学
無機化学

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10.1021/ic010499d

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@article{0fb95cd6f4ad454d92008711ac0ec194,

title = "Coordination-position isomeric MIICuIIand CuIIMII (M = Co, Ni, Zn) complexes derived from macrocyclic compartmental ligands",

abstract = "The dinucleating macrocydic ligands (L2;2)2- and (L2;3)2-, comprised of two 2-[(N-methylamino)methyl]-6-(iminomethyl)-4-bromophenolate entities combined by the -(CH2)2- chain between the two aminic nitrogen atoms and by the -(CH2)2- or -(CH2)3- chain between the two iminic nitrogen atoms, have afforded the following MIICuII complexes: [CoCu(L2;2)](ClO4)2·MeCN (1A), [NiCu(L2;2)](ClO4)2 (2A), [ZnCu(L2;2)](ClO4)2·0.5MeCN· EtOH (3A), [CoCu(L2;3)(MeCN)·(2-PrOH)](ClO4)2 (4A), [NiCu(L2;3)](ClO4)2 (5A), and [ZnCu(L2;3)](ClO4)2·1.5DMF (6A). [CoCu(L2;2)(MeCN)3](ClO4)2 (1A′) crystallizes in the monoclinic space group P21/n, a = 11.691(2) {\AA}, b = 18.572(3) {\AA}, c = 17.058(3) {\AA}, β = 91.18(2)°, V = 3703(1) {\AA}3, and Z = 4. [NiCu(L2;2)(DMF)2](ClO4)2 (2A′) crystallizes in the triclinic space group P{\=1}, a = 11.260(2) {\AA}, b = 16.359(6) {\AA}, c = 10.853(4) {\AA}, α = 96.98(3)°, β = 91.18(2)°, γ = 75.20(2)°, V = 1917(1) {\AA}3, and Z = 2. 4A crystallizes in the monoclinic space group P21/c1, a = 15.064(8) {\AA}, b = 11.434(5) {\AA}, c = 21.352(5) {\AA}, β = 95.83(2)°, V = 3659(2) {\AA}3, and Z = 4. The X-ray crystallographic results demonstrate the MII to reside in the N(amine)2O2 site and the CuII in the N(imine)2O2 site. The complexes 1-6 are regarded to be isomeric with [CuCo(L2;2))](ClO4)2·DMF (1B), [CuNi(L2;2))](ClO4)2·DMF·MeOH (2B), [CuZn(L2;2))](ClO4)2·H2O (3B)), [CuCo(L2;3))](ClO4)2·2H2O (4B), [CuNi(L2;3))](ClO4)2 (5B), and [CuZn(L2;3))](ClO4)2·H2O (6B) reported previously, when we ignore exogenous donating and solvating molecules. The isomeric MIICuII and CuIIMII complexes are differentiated by X-ray structural, magnetic, visible spectroscopic, and electrochemical studies. The two isomeric forms are significantly stabilized by the {"}macrocyclic effect{"} of the ligands, but 1A is converted into 1B on an electrode, and 2A is converted into 2B at elevated temperature.",

author = "Masami Yonemura and Keisuke Arimura and Koji Inoue and Naoki Usuki and Masaaki Ohba and Hisashi Okawa",

year = "2002",

month = feb,

day = "11",

doi = "10.1021/ic010499d",

language = "English",

volume = "41",

pages = "582--589",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "3",

}

TY - JOUR

T1 - Coordination-position isomeric MIICuIIand CuIIMII (M = Co, Ni, Zn) complexes derived from macrocyclic compartmental ligands

AU - Yonemura, Masami

AU - Arimura, Keisuke

AU - Inoue, Koji

AU - Usuki, Naoki

AU - Ohba, Masaaki

AU - Okawa, Hisashi

PY - 2002/2/11

Y1 - 2002/2/11

N2 - The dinucleating macrocydic ligands (L2;2)2- and (L2;3)2-, comprised of two 2-[(N-methylamino)methyl]-6-(iminomethyl)-4-bromophenolate entities combined by the -(CH2)2- chain between the two aminic nitrogen atoms and by the -(CH2)2- or -(CH2)3- chain between the two iminic nitrogen atoms, have afforded the following MIICuII complexes: [CoCu(L2;2)](ClO4)2·MeCN (1A), [NiCu(L2;2)](ClO4)2 (2A), [ZnCu(L2;2)](ClO4)2·0.5MeCN· EtOH (3A), [CoCu(L2;3)(MeCN)·(2-PrOH)](ClO4)2 (4A), [NiCu(L2;3)](ClO4)2 (5A), and [ZnCu(L2;3)](ClO4)2·1.5DMF (6A). [CoCu(L2;2)(MeCN)3](ClO4)2 (1A′) crystallizes in the monoclinic space group P21/n, a = 11.691(2) Å, b = 18.572(3) Å, c = 17.058(3) Å, β = 91.18(2)°, V = 3703(1) Å3, and Z = 4. [NiCu(L2;2)(DMF)2](ClO4)2 (2A′) crystallizes in the triclinic space group P1̄, a = 11.260(2) Å, b = 16.359(6) Å, c = 10.853(4) Å, α = 96.98(3)°, β = 91.18(2)°, γ = 75.20(2)°, V = 1917(1) Å3, and Z = 2. 4A crystallizes in the monoclinic space group P21/c1, a = 15.064(8) Å, b = 11.434(5) Å, c = 21.352(5) Å, β = 95.83(2)°, V = 3659(2) Å3, and Z = 4. The X-ray crystallographic results demonstrate the MII to reside in the N(amine)2O2 site and the CuII in the N(imine)2O2 site. The complexes 1-6 are regarded to be isomeric with [CuCo(L2;2))](ClO4)2·DMF (1B), [CuNi(L2;2))](ClO4)2·DMF·MeOH (2B), [CuZn(L2;2))](ClO4)2·H2O (3B)), [CuCo(L2;3))](ClO4)2·2H2O (4B), [CuNi(L2;3))](ClO4)2 (5B), and [CuZn(L2;3))](ClO4)2·H2O (6B) reported previously, when we ignore exogenous donating and solvating molecules. The isomeric MIICuII and CuIIMII complexes are differentiated by X-ray structural, magnetic, visible spectroscopic, and electrochemical studies. The two isomeric forms are significantly stabilized by the "macrocyclic effect" of the ligands, but 1A is converted into 1B on an electrode, and 2A is converted into 2B at elevated temperature.

AB - The dinucleating macrocydic ligands (L2;2)2- and (L2;3)2-, comprised of two 2-[(N-methylamino)methyl]-6-(iminomethyl)-4-bromophenolate entities combined by the -(CH2)2- chain between the two aminic nitrogen atoms and by the -(CH2)2- or -(CH2)3- chain between the two iminic nitrogen atoms, have afforded the following MIICuII complexes: [CoCu(L2;2)](ClO4)2·MeCN (1A), [NiCu(L2;2)](ClO4)2 (2A), [ZnCu(L2;2)](ClO4)2·0.5MeCN· EtOH (3A), [CoCu(L2;3)(MeCN)·(2-PrOH)](ClO4)2 (4A), [NiCu(L2;3)](ClO4)2 (5A), and [ZnCu(L2;3)](ClO4)2·1.5DMF (6A). [CoCu(L2;2)(MeCN)3](ClO4)2 (1A′) crystallizes in the monoclinic space group P21/n, a = 11.691(2) Å, b = 18.572(3) Å, c = 17.058(3) Å, β = 91.18(2)°, V = 3703(1) Å3, and Z = 4. [NiCu(L2;2)(DMF)2](ClO4)2 (2A′) crystallizes in the triclinic space group P1̄, a = 11.260(2) Å, b = 16.359(6) Å, c = 10.853(4) Å, α = 96.98(3)°, β = 91.18(2)°, γ = 75.20(2)°, V = 1917(1) Å3, and Z = 2. 4A crystallizes in the monoclinic space group P21/c1, a = 15.064(8) Å, b = 11.434(5) Å, c = 21.352(5) Å, β = 95.83(2)°, V = 3659(2) Å3, and Z = 4. The X-ray crystallographic results demonstrate the MII to reside in the N(amine)2O2 site and the CuII in the N(imine)2O2 site. The complexes 1-6 are regarded to be isomeric with [CuCo(L2;2))](ClO4)2·DMF (1B), [CuNi(L2;2))](ClO4)2·DMF·MeOH (2B), [CuZn(L2;2))](ClO4)2·H2O (3B)), [CuCo(L2;3))](ClO4)2·2H2O (4B), [CuNi(L2;3))](ClO4)2 (5B), and [CuZn(L2;3))](ClO4)2·H2O (6B) reported previously, when we ignore exogenous donating and solvating molecules. The isomeric MIICuII and CuIIMII complexes are differentiated by X-ray structural, magnetic, visible spectroscopic, and electrochemical studies. The two isomeric forms are significantly stabilized by the "macrocyclic effect" of the ligands, but 1A is converted into 1B on an electrode, and 2A is converted into 2B at elevated temperature.

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U2 - 10.1021/ic010499d

DO - 10.1021/ic010499d

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C2 - 11825087

AN - SCOPUS:0037060148

SN - 0020-1669

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EP - 589

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 3

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