Syntheses and characterizations of the Unsymmetrical Ligand (H2nypmpda) and Its Hexanuclear Nickel Complexes
碩士 === 國立臺灣大學 === 化學研究所 === 95 === Abstact The aim of this study is to investigate the synthesis, structures, and correlative properties of linear hexanickel metal string complexes, where the ligand is N- (1,8-naphthyridin-7-yl)-N’-(pyrimidin-2-yl)pyridine-2,6-diamine (H2nypmpda). One novel unsymmet...
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ndltd-TW-095NTU050650152015-12-07T04:03:59Z http://ndltd.ncl.edu.tw/handle/66285122051566562908 Syntheses and characterizations of the Unsymmetrical Ligand (H2nypmpda) and Its Hexanuclear Nickel Complexes 萘啶吡啶嘧啶二胺配基及其直線型六核金屬串錯合物之合成及研究 Yu-kai Huang 黃淯凱 碩士 國立臺灣大學 化學研究所 95 Abstact The aim of this study is to investigate the synthesis, structures, and correlative properties of linear hexanickel metal string complexes, where the ligand is N- (1,8-naphthyridin-7-yl)-N’-(pyrimidin-2-yl)pyridine-2,6-diamine (H2nypmpda). One novel unsymmetrical ligand (H2nypmpda) was synthesized by palladium-catalyzed cross-coupling of N-(6-bromopyridin-2-yl)-1,8-naphthyridin-2- amine (L2) with 2-aminopyrimidine. [Ni6(μ6-nypmpda)4Cl2](ClO4)2 (1) were synthesized by reaction of ligand H2nypmpda and nickel ion in melt naphthalene under basic condition. The one-electron reduced hexametal string complex [Ni6(μ 6-nypmpda)4Cl2]PF6 (2) was generated by reacting the hexanickel complex with the reductant N2H4. The structures of compounds 1 and 2 were characterized by single-crystal X-ray diffraction analysis. The X-ray structural studies reveal that the terminal nickel ions are five-coordinated and the inner nickel ions are four-coordinated. The difference in the structures 1 and 2 are the distances of Ni(1)-Ni(2) and Ni(2)-N, the Ni(1)-Ni(2) distance is shorter in 2 and Ni(2)-N distances are longer in 2. This attributes to the adding electron to dx2-y2 which is bonding to Ni(1)-Ni(2) and antibonding to Ni(2)-N bonds. The results of magnetic study show that complex 1 has a weak antiferromagnetic interaction between two terminal Ni(II) atoms and the coupling constant is -2.89 cm-1. Cyclic voltammetrical data show that complex 1 exhibits four couples ( E(red1) 1/2 = -0.07、E(red2) 1/2 = -0.24、E(red3) 1/2 = -0.46、E(red4) 1/2 = -0.68 ) and complex 2 has two couples ( E(red1) 1/2 = -0.08、E(red2) 1/2 = -0.63 ). These data indicate that complex 1 can be reduced easily. 彭旭明 2007 學位論文 ; thesis 64 zh-TW |
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碩士 === 國立臺灣大學 === 化學研究所 === 95 === Abstact
The aim of this study is to investigate the synthesis, structures, and correlative
properties of linear hexanickel metal string complexes, where the ligand is N-
(1,8-naphthyridin-7-yl)-N’-(pyrimidin-2-yl)pyridine-2,6-diamine (H2nypmpda).
One novel unsymmetrical ligand (H2nypmpda) was synthesized by
palladium-catalyzed cross-coupling of N-(6-bromopyridin-2-yl)-1,8-naphthyridin-2-
amine (L2) with 2-aminopyrimidine.
[Ni6(μ6-nypmpda)4Cl2](ClO4)2 (1) were synthesized by reaction of ligand
H2nypmpda and nickel ion in melt naphthalene under basic condition. The
one-electron reduced hexametal string complex [Ni6(μ 6-nypmpda)4Cl2]PF6 (2) was
generated by reacting the hexanickel complex with the reductant N2H4. The
structures of compounds 1 and 2 were characterized by single-crystal X-ray
diffraction analysis. The X-ray structural studies reveal that the terminal nickel ions
are five-coordinated and the inner nickel ions are four-coordinated. The difference
in the structures 1 and 2 are the distances of Ni(1)-Ni(2) and Ni(2)-N, the Ni(1)-Ni(2)
distance is shorter in 2 and Ni(2)-N distances are longer in 2. This attributes to the
adding electron to dx2-y2 which is bonding to Ni(1)-Ni(2) and antibonding to Ni(2)-N
bonds.
The results of magnetic study show that complex 1 has a weak antiferromagnetic
interaction between two terminal Ni(II) atoms and the coupling constant is -2.89 cm-1.
Cyclic voltammetrical data show that complex 1 exhibits four couples ( E(red1)
1/2
= -0.07、E(red2)
1/2 = -0.24、E(red3)
1/2 = -0.46、E(red4)
1/2 = -0.68 ) and complex 2 has two
couples ( E(red1)
1/2 = -0.08、E(red2)
1/2 = -0.63 ). These data indicate that complex 1 can be
reduced easily.
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author2 |
彭旭明 |
author_facet |
彭旭明 Yu-kai Huang 黃淯凱 |
author |
Yu-kai Huang 黃淯凱 |
spellingShingle |
Yu-kai Huang 黃淯凱 Syntheses and characterizations of the Unsymmetrical Ligand (H2nypmpda) and Its Hexanuclear Nickel Complexes |
author_sort |
Yu-kai Huang |
title |
Syntheses and characterizations of the Unsymmetrical Ligand (H2nypmpda) and Its Hexanuclear Nickel Complexes |
title_short |
Syntheses and characterizations of the Unsymmetrical Ligand (H2nypmpda) and Its Hexanuclear Nickel Complexes |
title_full |
Syntheses and characterizations of the Unsymmetrical Ligand (H2nypmpda) and Its Hexanuclear Nickel Complexes |
title_fullStr |
Syntheses and characterizations of the Unsymmetrical Ligand (H2nypmpda) and Its Hexanuclear Nickel Complexes |
title_full_unstemmed |
Syntheses and characterizations of the Unsymmetrical Ligand (H2nypmpda) and Its Hexanuclear Nickel Complexes |
title_sort |
syntheses and characterizations of the unsymmetrical ligand (h2nypmpda) and its hexanuclear nickel complexes |
publishDate |
2007 |
url |
http://ndltd.ncl.edu.tw/handle/66285122051566562908 |
work_keys_str_mv |
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