Tunable N-substitution in zwitterionic benzoquinonemonoimine derivatives: metal coordination, tandemlike synthesis of zwitterionic metal complexes, and supramolecular structures.
Tunable N-substitution in zwitterionic benzoquinonemonoimine derivatives: metal coordination, tandemlike synthesis of zwitterionic metal complexes, and supramolecular structures.
复制标题
两性离子苯醌单亚胺衍生物中可调节的N-取代：金属配位、两性离子金属配合物的串联合成和超分子结构。
作者：
Qing‐Zheng Yang;O. Siri;P. Braunstein
报道了用于合成两性离子 N,N-二烷基-2-氨基-5-醇化物-1,4-苯醌一亚胺衍生物 [C6H2(=NHR)2(=O)2] 5-16 的非常有效的氨基转移反应的完整细节。通过单晶 X 射线衍射确定了 5.H2O 中两性离子 5 (R=CH3)、13 (R=CH2CH2OMe)、15 (R=CH2CH2NMe2) 以及母体未取代系统 [C6H2(=NH2)2(=O)2] 4 在 4.H2O 中的分子结构。这种一锅法制备可以在水、MeOH或EtOH中进行，并允许获得带有N-取代基的新两性离子，这些取代基具有-OMe (13)、-OH (9-12)、R1 =或不等于R2 (14-16)的NR1R2或烯烃(8)等功能，从而产生丰富的配位化学，并允许对固态超分子排列进行微调。如之前对 15 的描述，其与 Zn(acac)2 反应得到八面体 Zn(II) 络合物 [Zn[C6H2(NCH2CH2NMe2)O(O)(NHCH2CH2NMe2)]2] (20)，配体 13 和 16 的配位“臂”与 Zn(acac)2 提供 2:1 加合物[Zn[C6H2(NCH2CH2X)O(=O)(NHCH2CH2NX)]2] 19 (X=OMe) 和 21 (X=NHEt)，分别在八面体 Zn(II) 中心周围具有 N2O4 和 N4O2 供体组。此外，两性离子 15 和 16 与 ZnCl2 反应，通过前所未有的串联反应，得到稳定的、具有晶体学特征的 Zn(II) 两性离子配合物 [ZnCl2[C6H2(NCH2CH2NR1R2)O(=O)(NHCH2CH2NHR1R2)]] 22 (R1=R2=Me) 和 23 (R1=Et, R2=H)合成其中 1) 有机苯醌一亚胺两性离子前体的两个侧氨基有利于金属配位和质子转移，2) 饱和连接体防止电荷之间的π共轭。无机（20、22、23）和有机（5、9、13 和 15）分子的固态结构排列性质由两性离子前体上 N-取代基性质的细微变化决定。
Full details on a very efficient transamination reaction for the synthesis of zwitterionic N,N-dialkyl-2-amino-5-alcoholate-1,4-benzoquinonemonoiminium derivatives [C6H2(=NHR)2(=O)2] 5-16 are reported. The molecular structures of zwitterions 5 (R=CH3) in 5.H2O, 13 (R=CH2CH2OMe), 15 (R=CH2CH2NMe2), and of the parent, unsubstituted system [C6H2(=NH2)2(=O)2] 4 in 4.H2O have been established by single-crystal X-ray diffraction. This one-pot preparation can be carried out in water, MeOH, or EtOH and allows access to new zwitterions with N-substituents bearing functionalities such as -OMe (13), -OH (9-12), NR1R2 with R1 = or not equal R2 (14-16) or an alkene (8), leading to a rich coordination chemistry and allowing fine-tuning of the supramolecular arrangements in the solid state. As previously described for 15, which reacted with Zn(acac)2 to afford the octahedral Zn(II) complex [Zn[C6H2(NCH2CH2NMe2)O(O)(NHCH2CH2NMe2)]2] (20), ligands 13 and 16 with coordinating "arms" afforded with Zn(acac)2 the 2:1 adducts [Zn[C6H2(NCH2CH2X)O(=O)(NHCH2CH2NX)]2] 19 (X=OMe) and 21 (X=NHEt), with N2O4 and N4O2 donor sets around the octahedral Zn(II) center, respectively. Furthermore, zwitterions 15 and 16 reacted with ZnCl2 to give the stable, crystallographically characterized Zn(II) zwitterionic complexes [ZnCl2[C6H2(NCH2CH2NR1R2)O(=O)(NHCH2CH2NHR1R2)]] 22 (R1=R2=Me) and 23 (R1=Et, R2=H) by means of an unprecedented, tandemlike synthesis in which 1) the two pendant amino groups of the organic benzoquinonemonoimine zwitterionic precursor favor metal coordination and proton transfer and 2) the saturated linker prevents pi-conjugation between the charges. The nature of the structural arrangements in the solid state for both inorganic (20, 22, 23) and organic (5, 9, 13, and 15) molecules is determined by subtle variations in the nature of the N-substituent on the zwitterion precursor.
醌依赖性血浆胺氧化酶对底物苯甲胺的催化周转导致 H2O2 依赖性失活：生成辅因子衍生的苯并恶唑的证据。
影响因子：
2.9
作者：
Lee,Y;Shepard,E;Smith,J;Dooley,DM;Sayre,LM
通讯作者：
Sayre,LM
影响因子：
15
作者：
Lee, Y;Ling, KQ;Sayre, LM
通讯作者：
Sayre, LM