Pseudohalide-bridged five-coordinate Ni(II) or Co(II) complexes with bulky bidentate ligands: Magneto-structural correlationship

Hui Zhong Kou, Shoko Hishiya, Osamu Sato

Research output: Contribution to journalArticle

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Abstract

Bidentate ligands 2,2′-biquinoline (biq) and 6,6′-dimethyl-2,2′-bipyridine (dmbpy) with steric hindrance substituents cis to the nitrogen atoms have been used in the synthesis of transition metal complexes. Six new doubly end-on azido-bridged binuclear complexes [M2(biq)21,1-N3)2(N3)2] (M = Ni (1), M = Co (2)), [M2(biq)21,1-N3)2Cl2] (M = Ni (3), M = Co (4)), [M2(dmbpy)21,1-N3)2(N3)2] (M = Ni (5), M = Co (6)) and one end-to-end thiocyanato-bridged polymeric [Ni(dmbpy)(μ1,3-SCN)(NCS)]n (7) have been synthesized and characterized by single crystal X-ray diffraction analysis and magnetic studies. Complexes 1-6 comprise five-coordinate M(II) ions bridged by two end-on azide ligands. The bridging M-N-M bond angles are in the small range 104.1-105.2°. Complex 7 consists of a singly thiocyanate-bridged Ni(II) chain in which Ni(II) ions are five-coordinate. This research suggests that the bulky ligands play a key role in the formation of five-coordinate coordination structure. All complexes display intramolecular intermetallic ferromagnetic coupling with JNiNi and JCoCo of ca. 23 or 13 cm-1 based on the Hamiltonian over(H, ^) = - 2 J over(S, ^)1 over(S, ^)2 (S1 = S2 = 1 for Ni2, or 3/2 for Co2). The singly SCN--bridged chainlike complex 7 shows intrachain ferromagnetic interaction with J = 3.96(2) cm-1 and D = -4.55(8) cm-1 (over(H, ^) = - 2 J ∑i = 1 (over(S, ̂)i over(S, ^)i + 1) - D ∑i = 1 [(over(S, ^)iZ)2 - 2 / 3]). Magneto-structural correlationship has been investigated.

Original languageEnglish
Pages (from-to)2396-2406
Number of pages11
JournalInorganica Chimica Acta
Volume361
Issue number8
DOIs
Publication statusPublished - Jun 2 2008

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Ligands
ligands
Ions
Hamiltonians
Azides
Coordination Complexes
Metal complexes
nitrogen atoms
X ray diffraction analysis
Intermetallics
Transition metals
intermetallics
ions
Nitrogen
transition metals
Single crystals
Atoms
single crystals
synthesis
diffraction

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Pseudohalide-bridged five-coordinate Ni(II) or Co(II) complexes with bulky bidentate ligands : Magneto-structural correlationship. / Kou, Hui Zhong; Hishiya, Shoko; Sato, Osamu.

In: Inorganica Chimica Acta, Vol. 361, No. 8, 02.06.2008, p. 2396-2406.

Research output: Contribution to journalArticle

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abstract = "Bidentate ligands 2,2′-biquinoline (biq) and 6,6′-dimethyl-2,2′-bipyridine (dmbpy) with steric hindrance substituents cis to the nitrogen atoms have been used in the synthesis of transition metal complexes. Six new doubly end-on azido-bridged binuclear complexes [M2(biq)2(μ1,1-N3)2(N3)2] (M = Ni (1), M = Co (2)), [M2(biq)2(μ1,1-N3)2Cl2] (M = Ni (3), M = Co (4)), [M2(dmbpy)2(μ1,1-N3)2(N3)2] (M = Ni (5), M = Co (6)) and one end-to-end thiocyanato-bridged polymeric [Ni(dmbpy)(μ1,3-SCN)(NCS)]n (7) have been synthesized and characterized by single crystal X-ray diffraction analysis and magnetic studies. Complexes 1-6 comprise five-coordinate M(II) ions bridged by two end-on azide ligands. The bridging M-N-M bond angles are in the small range 104.1-105.2°. Complex 7 consists of a singly thiocyanate-bridged Ni(II) chain in which Ni(II) ions are five-coordinate. This research suggests that the bulky ligands play a key role in the formation of five-coordinate coordination structure. All complexes display intramolecular intermetallic ferromagnetic coupling with JNiNi and JCoCo of ca. 23 or 13 cm-1 based on the Hamiltonian over(H, ^) = - 2 J over(S, ^)1 over(S, ^)2 (S1 = S2 = 1 for Ni2, or 3/2 for Co2). The singly SCN--bridged chainlike complex 7 shows intrachain ferromagnetic interaction with J = 3.96(2) cm-1 and D = -4.55(8) cm-1 (over(H, ^) = - 2 J ∑i = 1 (over(S, ̂)i over(S, ^)i + 1) - D ∑i = 1 [(over(S, ^)iZ)2 - 2 / 3]). Magneto-structural correlationship has been investigated.",
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T1 - Pseudohalide-bridged five-coordinate Ni(II) or Co(II) complexes with bulky bidentate ligands

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AU - Kou, Hui Zhong

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AU - Sato, Osamu

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N2 - Bidentate ligands 2,2′-biquinoline (biq) and 6,6′-dimethyl-2,2′-bipyridine (dmbpy) with steric hindrance substituents cis to the nitrogen atoms have been used in the synthesis of transition metal complexes. Six new doubly end-on azido-bridged binuclear complexes [M2(biq)2(μ1,1-N3)2(N3)2] (M = Ni (1), M = Co (2)), [M2(biq)2(μ1,1-N3)2Cl2] (M = Ni (3), M = Co (4)), [M2(dmbpy)2(μ1,1-N3)2(N3)2] (M = Ni (5), M = Co (6)) and one end-to-end thiocyanato-bridged polymeric [Ni(dmbpy)(μ1,3-SCN)(NCS)]n (7) have been synthesized and characterized by single crystal X-ray diffraction analysis and magnetic studies. Complexes 1-6 comprise five-coordinate M(II) ions bridged by two end-on azide ligands. The bridging M-N-M bond angles are in the small range 104.1-105.2°. Complex 7 consists of a singly thiocyanate-bridged Ni(II) chain in which Ni(II) ions are five-coordinate. This research suggests that the bulky ligands play a key role in the formation of five-coordinate coordination structure. All complexes display intramolecular intermetallic ferromagnetic coupling with JNiNi and JCoCo of ca. 23 or 13 cm-1 based on the Hamiltonian over(H, ^) = - 2 J over(S, ^)1 over(S, ^)2 (S1 = S2 = 1 for Ni2, or 3/2 for Co2). The singly SCN--bridged chainlike complex 7 shows intrachain ferromagnetic interaction with J = 3.96(2) cm-1 and D = -4.55(8) cm-1 (over(H, ^) = - 2 J ∑i = 1 (over(S, ̂)i over(S, ^)i + 1) - D ∑i = 1 [(over(S, ^)iZ)2 - 2 / 3]). Magneto-structural correlationship has been investigated.

AB - Bidentate ligands 2,2′-biquinoline (biq) and 6,6′-dimethyl-2,2′-bipyridine (dmbpy) with steric hindrance substituents cis to the nitrogen atoms have been used in the synthesis of transition metal complexes. Six new doubly end-on azido-bridged binuclear complexes [M2(biq)2(μ1,1-N3)2(N3)2] (M = Ni (1), M = Co (2)), [M2(biq)2(μ1,1-N3)2Cl2] (M = Ni (3), M = Co (4)), [M2(dmbpy)2(μ1,1-N3)2(N3)2] (M = Ni (5), M = Co (6)) and one end-to-end thiocyanato-bridged polymeric [Ni(dmbpy)(μ1,3-SCN)(NCS)]n (7) have been synthesized and characterized by single crystal X-ray diffraction analysis and magnetic studies. Complexes 1-6 comprise five-coordinate M(II) ions bridged by two end-on azide ligands. The bridging M-N-M bond angles are in the small range 104.1-105.2°. Complex 7 consists of a singly thiocyanate-bridged Ni(II) chain in which Ni(II) ions are five-coordinate. This research suggests that the bulky ligands play a key role in the formation of five-coordinate coordination structure. All complexes display intramolecular intermetallic ferromagnetic coupling with JNiNi and JCoCo of ca. 23 or 13 cm-1 based on the Hamiltonian over(H, ^) = - 2 J over(S, ^)1 over(S, ^)2 (S1 = S2 = 1 for Ni2, or 3/2 for Co2). The singly SCN--bridged chainlike complex 7 shows intrachain ferromagnetic interaction with J = 3.96(2) cm-1 and D = -4.55(8) cm-1 (over(H, ^) = - 2 J ∑i = 1 (over(S, ̂)i over(S, ^)i + 1) - D ∑i = 1 [(over(S, ^)iZ)2 - 2 / 3]). Magneto-structural correlationship has been investigated.

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