Monoprotic tetradentate N3O-donor ligands and their Cu(II) and Ni(II) complexes

Hongyan Luo, Jem Mau Lo, Phillip E. Fanwick, Joseph G. Stowell, Mark Green

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

A convenient four-step procedure was developed to prepare the novel monoprotic tetradentate ligands N-(2-hydroxy)benzyl-N-methyl-N′-(2-pyridyl)methyl-1,3-propanediamine (Hpamap) and N-(2-hydroxy)benzyl-N′-methylN′-(2-pyridyl)methyl-1,3-propanediamine (Hpmaap), which provide an N3O metal coordination sphere. A mononuclear copper(II) complex, [Cu(pamap)Cl] (A), was obtained by reaction of Hpamap with CuCl2·2H2O. The binuclear copper(II) complexes [Cu(pamap)]2(BF4)2 (B) and [Cu(pmaap)]2(BF4)2 (C) were obtained when these ligands were reacted with Cu(II) in the presence of the noncoordinating BF4- anion. Reaction of nickel(II) with the Hpamap ligand generated the binuclear Ni(II) complex [Ni2(pamap)2(NO3)]NO3 (D). The crystal of A (C17H22ClCuN3O) is orthorhombic Pbca (No. 61), a = 11.837(4) Å, b = 15.648(5) Å, c = 11.002(11) Å, Z = 8; that of B (C34H44B2Cu2F8N 6O2) is triclinic P1̄ (No. 2), a = 9.147(0) Å, b = 10.375(0) Å, c = 10.535(1) Å, a = 107.20(0)°, β= 91.19(0)°, γ = 105.05(0)°, Z = 1; that of C (C34H44B2Cu2F8N 6O2) is monoclinic P21/c (No. 14), a = 9.158(2) Å, b= 10.714(2) Å, c = 19.085(4) Å, ̊= 90.58(2)°, Z = 4; and that of D (C34H44N8NiO8) is monoclinic C2/c (No. 15), a = 13.849(0) Å b = 13.609(0) Å, c = 19.558(1) Å, β = 92.34 (0)°, Z = 4. The copper atoms of all three complexes are five-coordinate in the solid state, assuming the geometry of a distorted square pyramid with the deprotonated tetradentate ligand in the basal plane. The mononuclear complex A has a chloride ligand in the axial position, while each copper center in the binuclear complexes B and C has, in the axial position, a bridging phenolate O donor from the other unit of the dimer. Each nickel center in the binuclear complex D is six-coordinate, with the pseudo-octahedron formed by a deprotonated tetradentate ligand, a bridging nitrato oxygen atom, and a bridging phenoxy donor from the tetradentate ligand bound to the second nickel center.

Original languageEnglish (US)
Pages (from-to)2071-2078
Number of pages8
JournalInorganic Chemistry
Volume38
Issue number9
StatePublished - 1999
Externally publishedYes

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Ligands
ligands
Copper
Nickel
copper
nickel
Atoms
pyramids
Dimers
Anions
Chlorides
oxygen atoms
Metals
chlorides
dimers
Oxygen
anions
solid state
Crystals
Geometry

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Luo, H., Lo, J. M., Fanwick, P. E., Stowell, J. G., & Green, M. (1999). Monoprotic tetradentate N3O-donor ligands and their Cu(II) and Ni(II) complexes. Inorganic Chemistry, 38(9), 2071-2078.

Monoprotic tetradentate N3O-donor ligands and their Cu(II) and Ni(II) complexes. / Luo, Hongyan; Lo, Jem Mau; Fanwick, Phillip E.; Stowell, Joseph G.; Green, Mark.

In: Inorganic Chemistry, Vol. 38, No. 9, 1999, p. 2071-2078.

Research output: Contribution to journalArticle

Luo, H, Lo, JM, Fanwick, PE, Stowell, JG & Green, M 1999, 'Monoprotic tetradentate N3O-donor ligands and their Cu(II) and Ni(II) complexes', Inorganic Chemistry, vol. 38, no. 9, pp. 2071-2078.
Luo, Hongyan ; Lo, Jem Mau ; Fanwick, Phillip E. ; Stowell, Joseph G. ; Green, Mark. / Monoprotic tetradentate N3O-donor ligands and their Cu(II) and Ni(II) complexes. In: Inorganic Chemistry. 1999 ; Vol. 38, No. 9. pp. 2071-2078.
@article{22b3ecebf7ff445fb267363f5e7ccb1c,
title = "Monoprotic tetradentate N3O-donor ligands and their Cu(II) and Ni(II) complexes",
abstract = "A convenient four-step procedure was developed to prepare the novel monoprotic tetradentate ligands N-(2-hydroxy)benzyl-N-methyl-N′-(2-pyridyl)methyl-1,3-propanediamine (Hpamap) and N-(2-hydroxy)benzyl-N′-methylN′-(2-pyridyl)methyl-1,3-propanediamine (Hpmaap), which provide an N3O metal coordination sphere. A mononuclear copper(II) complex, [Cu(pamap)Cl] (A), was obtained by reaction of Hpamap with CuCl2·2H2O. The binuclear copper(II) complexes [Cu(pamap)]2(BF4)2 (B) and [Cu(pmaap)]2(BF4)2 (C) were obtained when these ligands were reacted with Cu(II) in the presence of the noncoordinating BF4- anion. Reaction of nickel(II) with the Hpamap ligand generated the binuclear Ni(II) complex [Ni2(pamap)2(NO3)]NO3 (D). The crystal of A (C17H22ClCuN3O) is orthorhombic Pbca (No. 61), a = 11.837(4) {\AA}, b = 15.648(5) {\AA}, c = 11.002(11) {\AA}, Z = 8; that of B (C34H44B2Cu2F8N 6O2) is triclinic P1̄ (No. 2), a = 9.147(0) {\AA}, b = 10.375(0) {\AA}, c = 10.535(1) {\AA}, a = 107.20(0)°, β= 91.19(0)°, γ = 105.05(0)°, Z = 1; that of C (C34H44B2Cu2F8N 6O2) is monoclinic P21/c (No. 14), a = 9.158(2) {\AA}, b= 10.714(2) {\AA}, c = 19.085(4) {\AA}, ̊= 90.58(2)°, Z = 4; and that of D (C34H44N8NiO8) is monoclinic C2/c (No. 15), a = 13.849(0) {\AA} b = 13.609(0) {\AA}, c = 19.558(1) {\AA}, β = 92.34 (0)°, Z = 4. The copper atoms of all three complexes are five-coordinate in the solid state, assuming the geometry of a distorted square pyramid with the deprotonated tetradentate ligand in the basal plane. The mononuclear complex A has a chloride ligand in the axial position, while each copper center in the binuclear complexes B and C has, in the axial position, a bridging phenolate O donor from the other unit of the dimer. Each nickel center in the binuclear complex D is six-coordinate, with the pseudo-octahedron formed by a deprotonated tetradentate ligand, a bridging nitrato oxygen atom, and a bridging phenoxy donor from the tetradentate ligand bound to the second nickel center.",
author = "Hongyan Luo and Lo, {Jem Mau} and Fanwick, {Phillip E.} and Stowell, {Joseph G.} and Mark Green",
year = "1999",
language = "English (US)",
volume = "38",
pages = "2071--2078",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "9",

}

TY - JOUR

T1 - Monoprotic tetradentate N3O-donor ligands and their Cu(II) and Ni(II) complexes

AU - Luo, Hongyan

AU - Lo, Jem Mau

AU - Fanwick, Phillip E.

AU - Stowell, Joseph G.

AU - Green, Mark

PY - 1999

Y1 - 1999

N2 - A convenient four-step procedure was developed to prepare the novel monoprotic tetradentate ligands N-(2-hydroxy)benzyl-N-methyl-N′-(2-pyridyl)methyl-1,3-propanediamine (Hpamap) and N-(2-hydroxy)benzyl-N′-methylN′-(2-pyridyl)methyl-1,3-propanediamine (Hpmaap), which provide an N3O metal coordination sphere. A mononuclear copper(II) complex, [Cu(pamap)Cl] (A), was obtained by reaction of Hpamap with CuCl2·2H2O. The binuclear copper(II) complexes [Cu(pamap)]2(BF4)2 (B) and [Cu(pmaap)]2(BF4)2 (C) were obtained when these ligands were reacted with Cu(II) in the presence of the noncoordinating BF4- anion. Reaction of nickel(II) with the Hpamap ligand generated the binuclear Ni(II) complex [Ni2(pamap)2(NO3)]NO3 (D). The crystal of A (C17H22ClCuN3O) is orthorhombic Pbca (No. 61), a = 11.837(4) Å, b = 15.648(5) Å, c = 11.002(11) Å, Z = 8; that of B (C34H44B2Cu2F8N 6O2) is triclinic P1̄ (No. 2), a = 9.147(0) Å, b = 10.375(0) Å, c = 10.535(1) Å, a = 107.20(0)°, β= 91.19(0)°, γ = 105.05(0)°, Z = 1; that of C (C34H44B2Cu2F8N 6O2) is monoclinic P21/c (No. 14), a = 9.158(2) Å, b= 10.714(2) Å, c = 19.085(4) Å, ̊= 90.58(2)°, Z = 4; and that of D (C34H44N8NiO8) is monoclinic C2/c (No. 15), a = 13.849(0) Å b = 13.609(0) Å, c = 19.558(1) Å, β = 92.34 (0)°, Z = 4. The copper atoms of all three complexes are five-coordinate in the solid state, assuming the geometry of a distorted square pyramid with the deprotonated tetradentate ligand in the basal plane. The mononuclear complex A has a chloride ligand in the axial position, while each copper center in the binuclear complexes B and C has, in the axial position, a bridging phenolate O donor from the other unit of the dimer. Each nickel center in the binuclear complex D is six-coordinate, with the pseudo-octahedron formed by a deprotonated tetradentate ligand, a bridging nitrato oxygen atom, and a bridging phenoxy donor from the tetradentate ligand bound to the second nickel center.

AB - A convenient four-step procedure was developed to prepare the novel monoprotic tetradentate ligands N-(2-hydroxy)benzyl-N-methyl-N′-(2-pyridyl)methyl-1,3-propanediamine (Hpamap) and N-(2-hydroxy)benzyl-N′-methylN′-(2-pyridyl)methyl-1,3-propanediamine (Hpmaap), which provide an N3O metal coordination sphere. A mononuclear copper(II) complex, [Cu(pamap)Cl] (A), was obtained by reaction of Hpamap with CuCl2·2H2O. The binuclear copper(II) complexes [Cu(pamap)]2(BF4)2 (B) and [Cu(pmaap)]2(BF4)2 (C) were obtained when these ligands were reacted with Cu(II) in the presence of the noncoordinating BF4- anion. Reaction of nickel(II) with the Hpamap ligand generated the binuclear Ni(II) complex [Ni2(pamap)2(NO3)]NO3 (D). The crystal of A (C17H22ClCuN3O) is orthorhombic Pbca (No. 61), a = 11.837(4) Å, b = 15.648(5) Å, c = 11.002(11) Å, Z = 8; that of B (C34H44B2Cu2F8N 6O2) is triclinic P1̄ (No. 2), a = 9.147(0) Å, b = 10.375(0) Å, c = 10.535(1) Å, a = 107.20(0)°, β= 91.19(0)°, γ = 105.05(0)°, Z = 1; that of C (C34H44B2Cu2F8N 6O2) is monoclinic P21/c (No. 14), a = 9.158(2) Å, b= 10.714(2) Å, c = 19.085(4) Å, ̊= 90.58(2)°, Z = 4; and that of D (C34H44N8NiO8) is monoclinic C2/c (No. 15), a = 13.849(0) Å b = 13.609(0) Å, c = 19.558(1) Å, β = 92.34 (0)°, Z = 4. The copper atoms of all three complexes are five-coordinate in the solid state, assuming the geometry of a distorted square pyramid with the deprotonated tetradentate ligand in the basal plane. The mononuclear complex A has a chloride ligand in the axial position, while each copper center in the binuclear complexes B and C has, in the axial position, a bridging phenolate O donor from the other unit of the dimer. Each nickel center in the binuclear complex D is six-coordinate, with the pseudo-octahedron formed by a deprotonated tetradentate ligand, a bridging nitrato oxygen atom, and a bridging phenoxy donor from the tetradentate ligand bound to the second nickel center.

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