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鈷、鎳及銅1，8-含氮雜環碳烯卡唑金屬錯化合物之合成、結構及反應性探討 ...

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鈷、鎳及銅1，8-含氮雜環碳烯卡唑金屬錯化合物之合成、結構及反應性探討 = The Study of Synthesis, Structure and Reactivity of Cobalt,Nickel and Copper 1,8-Bis(N-Heterocyclic Carbene)carbazolide Complexes

Record Type:	Language materials, printed : monographic
Paralel Title:	The Study of Synthesis, Structure and Reactivity of Cobalt,Nickel and Copper 1,8-Bis(N-Heterocyclic Carbene)carbazolide Complexes
Author:	范介妮,
Secondary Intellectual Responsibility:	國立高雄大學
Place of Publication:	[高雄市]
Published:	撰者;
Year of Publication:	2010[民99]
Description:	114面圖，表 : 30公分;
Subject:	卡唑
Subject:	Cobalt
Online resource:	http://handle.ncl.edu.tw/11296/ndltd/18040306875654356972
[NT 15001349]:	鈷鎳及銅1,8-含氮雜環碳烯卡唑金屬錯化合物之合成結構及反應性探討
Summary:	以含氮雜環碳烯卡唑配位基與金屬之醋酸或鹵素衍生物經由錯化反應可以得到一系列pincer-type 含氮雜環碳烯(N-hetereocyclic carbene)卡唑金屬錯化合物。此類金屬錯化合物會因其金屬不同而造成配位型態不同。其中鈷金屬錯化合物 (4e-6e) 的固態分子結構由X-ray 單晶體繞射分析知此錯化合物為六配位’Co(III)’雙配位基結構。另外鎳金屬錯化合物由X-ray 單晶繞射得知為四配位Ni(II)單配位基結構 (4b-6b,4c-6c) 。銅金屬錯化合物 (4d-6d)以質譜儀分析推測可能結構為類似鎳金屬錯化合物之四配位Cu(II)結構。在化性方面，鎳金屬錯化合物 (4a-6a) 在氧氣下與氰基烷和鹼基反應，經由氰基烷之C-CN 斷鍵可形成氰基鎳金屬錯化合物 (4f-6f)。經由反應機制探討，推測鹼基應先與氰基烷進行去質子化再與氧氣以及鎳金屬進行斷鍵反應。氣相層\析質譜儀以及氣相層析儀分析其氰基烷斷鍵後之產物，其中雙聚物的出現可發現在此反應中會涉及到碳與碳的成鍵與斷鍵作用。在物性方面，銅與配位基的鍵結會增強配位基在373nm的放光效應。 A series of cobalt, nickel and copper 1,8-bis(imidazol-1-yl) carbazolide compoundswere prepared by complexation of 1,8-bis(imidazol-1-yl) carbazolide ligands with metal acetates or halides. Their molecular structures strongly depend on the central metal atoms. By X-ray diffraction crystallography analysis, the cobalt atom in the complexes exhibits a six-coordinated octahedral geometry, in which two 1,8-bis(imidazol-1-yl) carbazolide ligands attach to the Co(III) ion with two N atoms of the carbazole in cis position. On the other hand, the nickel complexes possess a twisted square planar geometry for the central Ni (II) ion. Moreover, the cobalt and nickel complexes have been fully characterized by 1H NMR, 13C NMR, EA, MASS.According to the analysis of MASS, the copper derivatives might have the molecular structures to similar to the nickel analogs.The Nickel 1,8-bis(imidazol-1-yl)carbazolide complexes may react with alkylnitrile under basic and aerobic.Condition to form nickel cyanide complexes. The study of the mechanism of this reaction show that deprotonation of alkylnitrile would be the first step of the reaction. The observation of benzil indicates that both C-C bond breaking and formation would occur during the reaction. Optical study also shows the metal complexation would enhance the efficiency of the photoluminescence of 1,8-bis(imidazol-1-yl)carbazolide in the cases of copper complexes.

鈷、鎳及銅1，8-含氮雜環碳烯卡唑金屬錯化合物之合成、結構及反應性探討 = The Study of Synthesis, Structure and Reactivity of Cobalt,Nickel and Copper 1,8-Bis(N-Heterocyclic Carbene)carbazolide Complexes
范, 介妮

鈷、鎳及銅1，8-含氮雜環碳烯卡唑金屬錯化合物之合成、結構及反應性探討 = The Study of Synthesis, Structure and Reactivity of Cobalt,Nickel and Copper 1,8-Bis(N-Heterocyclic Carbene)carbazolide Complexes / 范介妮撰 - [高雄市] : 撰者, 2010[民99]. - 114面 ; 圖，表 ; 30公分.
參考書目：面96-100.
卡唑Cobalt

鈷、鎳及銅1，8-含氮雜環碳烯卡唑金屬錯化合物之合成、結構及反應性探討 = The Study of Synthesis, Structure and Reactivity of Cobalt,Nickel and Copper 1,8-Bis(N-Heterocyclic Carbene)carbazolide Complexes
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330 $a 以含氮雜環碳烯卡唑配位基與金屬之醋酸或鹵素衍生物經由錯化反應可以得到一系列pincer-type 含氮雜環碳烯(N-hetereocyclic carbene)卡唑金屬錯化合物。此類金屬錯化合物會因其金屬不同而造成配位型態不同。其中鈷金屬錯化合物 (4e-6e) 的固態分子結構由X-ray 單晶體繞射分析知此錯化合物為六配位’Co(III)’雙配位基結構。另外鎳金屬錯化合物由X-ray 單晶繞射得知為四配位Ni(II)單配位基結構 (4b-6b,4c-6c) 。銅金屬錯化合物 (4d-6d)以質譜儀分析推測可能結構為類似鎳金屬錯化合物之四配位Cu(II)結構。在化性方面，鎳金屬錯化合物 (4a-6a) 在氧氣下與氰基烷和鹼基反應，經由氰基烷之C-CN 斷鍵可形成氰基鎳金屬錯化合物 (4f-6f)。經由反應機制探討，推測鹼基應先與氰基烷進行去質子化再與氧氣以及鎳金屬進行斷鍵反應。氣相層\析質譜儀以及氣相層析儀分析其氰基烷斷鍵後之產物，其中雙聚物的出現可發現在此反應中會涉及到碳與碳的成鍵與斷鍵作用。在物性方面，銅與配位基的鍵結會增強配位基在373nm的放光效應。 A series of cobalt, nickel and copper 1,8-bis(imidazol-1-yl) carbazolide compoundswere prepared by complexation of 1,8-bis(imidazol-1-yl) carbazolide ligands with metal acetates or halides. Their molecular structures strongly depend on the central metal atoms. By X-ray diffraction crystallography analysis, the cobalt atom in the complexes exhibits a six-coordinated octahedral geometry, in which two 1,8-bis(imidazol-1-yl) carbazolide ligands attach to the Co(III) ion with two N atoms of the carbazole in cis position. On the other hand, the nickel complexes possess a twisted square planar geometry for the central Ni (II) ion. Moreover, the cobalt and nickel complexes have been fully characterized by 1H NMR, 13C NMR, EA, MASS.According to the analysis of MASS, the copper derivatives might have the molecular structures to similar to the nickel analogs.The Nickel 1,8-bis(imidazol-1-yl)carbazolide complexes may react with alkylnitrile under basic and aerobic.Condition to form nickel cyanide complexes. The study of the mechanism of this reaction show that deprotonation of alkylnitrile would be the first step of the reaction. The observation of benzil indicates that both C-C bond breaking and formation would occur during the reaction. Optical study also shows the metal complexation would enhance the efficiency of the photoluminescence of 1,8-bis(imidazol-1-yl)carbazolide in the cases of copper complexes.
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