Binucleating macrocyclic [14]N4 ligands and their complexes. Synthesis of the free ligand 2,3-dioxo-5,6

13,14-dibenzo-9,10-(4′,5′-dimethylbenzo)-1,4,8,11- tetraazacyclotetradeca-7,11-diene (L) and of the 7,12-Me2-L metal complexes and derivatives. Crystal structures and properties of the [M′][M(7,12-Me2-L)] complexes (M = ...

D. Christodoulou, Mercouri G Kanatzidis, D. Coucouvanis

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Abstract

Full title: Binucleating macrocyclic [14]N4 ligands and their complexes. Synthesis of the free ligand 2,3-dioxo-5,6:13,14-dibenzo-9,10-(4′,5′-dimethylbenzo)-1,4,8,11- tetraazacyclotetradeca-7,11-diene (L) and of the 7,12-Me2-L metal complexes and derivatives. Crystal structures and properties of the [M′][M(7,12-Me2-L)] complexes (M = Ni(II); M = Co(II); M′ = ZnCl2, M = Ni(II); M′ = [Na(5-crown-15)]+, M = Ni(II); M′ = [(C2H5)4N]+, M = Ni(II)). The free macrocyclic ligand 2,3-dioxo-5,6:13,14-dibenzo-9,10-(4′,5′-dimethylbenzo)-1,4,8,11- tetraazacyclotetradeca-7,11-diene, abbreviated α-diketo-TAD-Me2, and its complexes with Ni(II) and Co(II) have been synthesized. The Ni(II) complex readily undergoes reduction and by virtue of the α-diketone function, appended to the macrocyclic ring, can bind to other metal ions. Complexes of the 2,3-dioxo-5,6:13,14-dibenzo-7,12-dimethyl-9,10-(4′,5′-dimethylbenzo) -1,4,8,11-tetraazacyclotetradeca-7,11-diene, abbreviated α-diketo-TAD-Me4, also have been synthesized. The structures of Ni(α-diketo-TAD-Me4) (IVa), of the reduction derivatives (Et4N)[Ni(α-diketo-TAD-Me4+H)] (V) and [Na(5-crown-15)][Ni(α-diketo-TAD-Me4+H)] (VI), and of the binuclear complex [Ni(α-diketo-TAD-Me4)]ZnCl2 (VII) are reported. Crystals of IVa are orthorhombic, space group Pnam; a = 7.934 (4) Å, b = 12.663 (6) Å, and c = 20.922 (9) Å. Crystals of V are monoclinic, space group P21/a; a = 14.789 (6) Å, b = 17.582 (5) Å, c = 15.372 (6) Å, and β = 108.36 (3)°. Crystals of VI are monoclinic, space group P21/n; a = 17.201 (11) Å, b = 12.113 (11) Å, c = 17.426 (12) Å, and β = 75.32 (5)°. Crystals of VII are monoclinic, space group P21/c; a = 11.139 (9) Å, b = 16.19 (2) Å, c = 16.15 (1) Å, and β = 98.03 (7)°. Refinements by full-matrix least squares of 151 parameters on 1085 data for IVa, of 371 parameters on 2455 data for V, of 349 parameters on 2440 data for VI, and of 215 parameters on 1514 data for VII converged to the R values of 0.044, 0.073, 0.078, and 0.073, respectively. In all structures the hydrogen atoms were included in the structure factor calculations but were not refined. In IVa the macrocycle adopts a saddle-shaped conformation and the molecules stack along the crystallographic a axis. The planar NiN4 chromophores are equally spaced with a Ni-Ni distance of 4.059 (1) Å. In V and VI the reduction has resulted in the saturation of one of the imino bonds, and in the structure of VI the Na+ ion is coordinated by the α-diketo function and is found at 5.070 (9) Å from the Ni atom. In VII the Zn atom also is coordinated by the α-diketo function and is located 5.140 (3) Å from the Ni atom. The electrochemistry and electronic spectra of the complexes are reported. Co(α-diketo-TAD-Me2), which is a high-spin, square-planar Co(II) complex, shows a quasireversible reduction at -0.86 V vs SCE and binds O2 reversibly.

Original languageEnglish
Pages (from-to)191-201
Number of pages11
JournalInorganic Chemistry
Volume29
Issue number2
Publication statusPublished - 1990

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Coordination Complexes
dienes
Crystal structure
Ligands
Derivatives
Atoms
Crystals
ligands
crystal structure
synthesis
metals
crystals
atoms
saddles
Electrochemistry
Chromophores
electrochemistry
electronic spectra
chromophores
Metal ions

ASJC Scopus subject areas

  • Inorganic Chemistry

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@article{1d601aebfc4a47f4854c1ec0f26a6c99,
title = "Binucleating macrocyclic [14]N4 ligands and their complexes. Synthesis of the free ligand 2,3-dioxo-5,6: 13,14-dibenzo-9,10-(4′,5′-dimethylbenzo)-1,4,8,11- tetraazacyclotetradeca-7,11-diene (L) and of the 7,12-Me2-L metal complexes and derivatives. Crystal structures and properties of the [M′][M(7,12-Me2-L)] complexes (M = ...",
abstract = "Full title: Binucleating macrocyclic [14]N4 ligands and their complexes. Synthesis of the free ligand 2,3-dioxo-5,6:13,14-dibenzo-9,10-(4′,5′-dimethylbenzo)-1,4,8,11- tetraazacyclotetradeca-7,11-diene (L) and of the 7,12-Me2-L metal complexes and derivatives. Crystal structures and properties of the [M′][M(7,12-Me2-L)] complexes (M = Ni(II); M = Co(II); M′ = ZnCl2, M = Ni(II); M′ = [Na(5-crown-15)]+, M = Ni(II); M′ = [(C2H5)4N]+, M = Ni(II)). The free macrocyclic ligand 2,3-dioxo-5,6:13,14-dibenzo-9,10-(4′,5′-dimethylbenzo)-1,4,8,11- tetraazacyclotetradeca-7,11-diene, abbreviated α-diketo-TAD-Me2, and its complexes with Ni(II) and Co(II) have been synthesized. The Ni(II) complex readily undergoes reduction and by virtue of the α-diketone function, appended to the macrocyclic ring, can bind to other metal ions. Complexes of the 2,3-dioxo-5,6:13,14-dibenzo-7,12-dimethyl-9,10-(4′,5′-dimethylbenzo) -1,4,8,11-tetraazacyclotetradeca-7,11-diene, abbreviated α-diketo-TAD-Me4, also have been synthesized. The structures of Ni(α-diketo-TAD-Me4) (IVa), of the reduction derivatives (Et4N)[Ni(α-diketo-TAD-Me4+H)] (V) and [Na(5-crown-15)][Ni(α-diketo-TAD-Me4+H)] (VI), and of the binuclear complex [Ni(α-diketo-TAD-Me4)]ZnCl2 (VII) are reported. Crystals of IVa are orthorhombic, space group Pnam; a = 7.934 (4) {\AA}, b = 12.663 (6) {\AA}, and c = 20.922 (9) {\AA}. Crystals of V are monoclinic, space group P21/a; a = 14.789 (6) {\AA}, b = 17.582 (5) {\AA}, c = 15.372 (6) {\AA}, and β = 108.36 (3)°. Crystals of VI are monoclinic, space group P21/n; a = 17.201 (11) {\AA}, b = 12.113 (11) {\AA}, c = 17.426 (12) {\AA}, and β = 75.32 (5)°. Crystals of VII are monoclinic, space group P21/c; a = 11.139 (9) {\AA}, b = 16.19 (2) {\AA}, c = 16.15 (1) {\AA}, and β = 98.03 (7)°. Refinements by full-matrix least squares of 151 parameters on 1085 data for IVa, of 371 parameters on 2455 data for V, of 349 parameters on 2440 data for VI, and of 215 parameters on 1514 data for VII converged to the R values of 0.044, 0.073, 0.078, and 0.073, respectively. In all structures the hydrogen atoms were included in the structure factor calculations but were not refined. In IVa the macrocycle adopts a saddle-shaped conformation and the molecules stack along the crystallographic a axis. The planar NiN4 chromophores are equally spaced with a Ni-Ni distance of 4.059 (1) {\AA}. In V and VI the reduction has resulted in the saturation of one of the imino bonds, and in the structure of VI the Na+ ion is coordinated by the α-diketo function and is found at 5.070 (9) {\AA} from the Ni atom. In VII the Zn atom also is coordinated by the α-diketo function and is located 5.140 (3) {\AA} from the Ni atom. The electrochemistry and electronic spectra of the complexes are reported. Co(α-diketo-TAD-Me2), which is a high-spin, square-planar Co(II) complex, shows a quasireversible reduction at -0.86 V vs SCE and binds O2 reversibly.",
author = "D. Christodoulou and Kanatzidis, {Mercouri G} and D. Coucouvanis",
year = "1990",
language = "English",
volume = "29",
pages = "191--201",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - Binucleating macrocyclic [14]N4 ligands and their complexes. Synthesis of the free ligand 2,3-dioxo-5,6

T2 - 13,14-dibenzo-9,10-(4′,5′-dimethylbenzo)-1,4,8,11- tetraazacyclotetradeca-7,11-diene (L) and of the 7,12-Me2-L metal complexes and derivatives. Crystal structures and properties of the [M′][M(7,12-Me2-L)] complexes (M = ...

AU - Christodoulou, D.

AU - Kanatzidis, Mercouri G

AU - Coucouvanis, D.

PY - 1990

Y1 - 1990

N2 - Full title: Binucleating macrocyclic [14]N4 ligands and their complexes. Synthesis of the free ligand 2,3-dioxo-5,6:13,14-dibenzo-9,10-(4′,5′-dimethylbenzo)-1,4,8,11- tetraazacyclotetradeca-7,11-diene (L) and of the 7,12-Me2-L metal complexes and derivatives. Crystal structures and properties of the [M′][M(7,12-Me2-L)] complexes (M = Ni(II); M = Co(II); M′ = ZnCl2, M = Ni(II); M′ = [Na(5-crown-15)]+, M = Ni(II); M′ = [(C2H5)4N]+, M = Ni(II)). The free macrocyclic ligand 2,3-dioxo-5,6:13,14-dibenzo-9,10-(4′,5′-dimethylbenzo)-1,4,8,11- tetraazacyclotetradeca-7,11-diene, abbreviated α-diketo-TAD-Me2, and its complexes with Ni(II) and Co(II) have been synthesized. The Ni(II) complex readily undergoes reduction and by virtue of the α-diketone function, appended to the macrocyclic ring, can bind to other metal ions. Complexes of the 2,3-dioxo-5,6:13,14-dibenzo-7,12-dimethyl-9,10-(4′,5′-dimethylbenzo) -1,4,8,11-tetraazacyclotetradeca-7,11-diene, abbreviated α-diketo-TAD-Me4, also have been synthesized. The structures of Ni(α-diketo-TAD-Me4) (IVa), of the reduction derivatives (Et4N)[Ni(α-diketo-TAD-Me4+H)] (V) and [Na(5-crown-15)][Ni(α-diketo-TAD-Me4+H)] (VI), and of the binuclear complex [Ni(α-diketo-TAD-Me4)]ZnCl2 (VII) are reported. Crystals of IVa are orthorhombic, space group Pnam; a = 7.934 (4) Å, b = 12.663 (6) Å, and c = 20.922 (9) Å. Crystals of V are monoclinic, space group P21/a; a = 14.789 (6) Å, b = 17.582 (5) Å, c = 15.372 (6) Å, and β = 108.36 (3)°. Crystals of VI are monoclinic, space group P21/n; a = 17.201 (11) Å, b = 12.113 (11) Å, c = 17.426 (12) Å, and β = 75.32 (5)°. Crystals of VII are monoclinic, space group P21/c; a = 11.139 (9) Å, b = 16.19 (2) Å, c = 16.15 (1) Å, and β = 98.03 (7)°. Refinements by full-matrix least squares of 151 parameters on 1085 data for IVa, of 371 parameters on 2455 data for V, of 349 parameters on 2440 data for VI, and of 215 parameters on 1514 data for VII converged to the R values of 0.044, 0.073, 0.078, and 0.073, respectively. In all structures the hydrogen atoms were included in the structure factor calculations but were not refined. In IVa the macrocycle adopts a saddle-shaped conformation and the molecules stack along the crystallographic a axis. The planar NiN4 chromophores are equally spaced with a Ni-Ni distance of 4.059 (1) Å. In V and VI the reduction has resulted in the saturation of one of the imino bonds, and in the structure of VI the Na+ ion is coordinated by the α-diketo function and is found at 5.070 (9) Å from the Ni atom. In VII the Zn atom also is coordinated by the α-diketo function and is located 5.140 (3) Å from the Ni atom. The electrochemistry and electronic spectra of the complexes are reported. Co(α-diketo-TAD-Me2), which is a high-spin, square-planar Co(II) complex, shows a quasireversible reduction at -0.86 V vs SCE and binds O2 reversibly.

AB - Full title: Binucleating macrocyclic [14]N4 ligands and their complexes. Synthesis of the free ligand 2,3-dioxo-5,6:13,14-dibenzo-9,10-(4′,5′-dimethylbenzo)-1,4,8,11- tetraazacyclotetradeca-7,11-diene (L) and of the 7,12-Me2-L metal complexes and derivatives. Crystal structures and properties of the [M′][M(7,12-Me2-L)] complexes (M = Ni(II); M = Co(II); M′ = ZnCl2, M = Ni(II); M′ = [Na(5-crown-15)]+, M = Ni(II); M′ = [(C2H5)4N]+, M = Ni(II)). The free macrocyclic ligand 2,3-dioxo-5,6:13,14-dibenzo-9,10-(4′,5′-dimethylbenzo)-1,4,8,11- tetraazacyclotetradeca-7,11-diene, abbreviated α-diketo-TAD-Me2, and its complexes with Ni(II) and Co(II) have been synthesized. The Ni(II) complex readily undergoes reduction and by virtue of the α-diketone function, appended to the macrocyclic ring, can bind to other metal ions. Complexes of the 2,3-dioxo-5,6:13,14-dibenzo-7,12-dimethyl-9,10-(4′,5′-dimethylbenzo) -1,4,8,11-tetraazacyclotetradeca-7,11-diene, abbreviated α-diketo-TAD-Me4, also have been synthesized. The structures of Ni(α-diketo-TAD-Me4) (IVa), of the reduction derivatives (Et4N)[Ni(α-diketo-TAD-Me4+H)] (V) and [Na(5-crown-15)][Ni(α-diketo-TAD-Me4+H)] (VI), and of the binuclear complex [Ni(α-diketo-TAD-Me4)]ZnCl2 (VII) are reported. Crystals of IVa are orthorhombic, space group Pnam; a = 7.934 (4) Å, b = 12.663 (6) Å, and c = 20.922 (9) Å. Crystals of V are monoclinic, space group P21/a; a = 14.789 (6) Å, b = 17.582 (5) Å, c = 15.372 (6) Å, and β = 108.36 (3)°. Crystals of VI are monoclinic, space group P21/n; a = 17.201 (11) Å, b = 12.113 (11) Å, c = 17.426 (12) Å, and β = 75.32 (5)°. Crystals of VII are monoclinic, space group P21/c; a = 11.139 (9) Å, b = 16.19 (2) Å, c = 16.15 (1) Å, and β = 98.03 (7)°. Refinements by full-matrix least squares of 151 parameters on 1085 data for IVa, of 371 parameters on 2455 data for V, of 349 parameters on 2440 data for VI, and of 215 parameters on 1514 data for VII converged to the R values of 0.044, 0.073, 0.078, and 0.073, respectively. In all structures the hydrogen atoms were included in the structure factor calculations but were not refined. In IVa the macrocycle adopts a saddle-shaped conformation and the molecules stack along the crystallographic a axis. The planar NiN4 chromophores are equally spaced with a Ni-Ni distance of 4.059 (1) Å. In V and VI the reduction has resulted in the saturation of one of the imino bonds, and in the structure of VI the Na+ ion is coordinated by the α-diketo function and is found at 5.070 (9) Å from the Ni atom. In VII the Zn atom also is coordinated by the α-diketo function and is located 5.140 (3) Å from the Ni atom. The electrochemistry and electronic spectra of the complexes are reported. Co(α-diketo-TAD-Me2), which is a high-spin, square-planar Co(II) complex, shows a quasireversible reduction at -0.86 V vs SCE and binds O2 reversibly.

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