Synthesis of dinitrosyl iron complexes (DNICs) with intramolecular hydrogen bonding
Synthesis of dinitrosyl iron complexes (DNICs) with intramolecular hydrogen bonding
复制标题
DOI：
10.1016/j.jorganchem.2008.08.034
复制
发表时间：
2008-11-15
影响因子：
2.3
通讯作者：
Chang, Chih-Ming
中科院分区：
文献类型：
--
作者：
Chiou, Show-Jen;Wang, Chien-Chu;Chang, Chih-Ming
制备了含肽键的HSCH 2CONHCH 3和HSCH 2CON（CH 3）（2），分别用于合成具有和不具有分子内氢键的DNIC。[（NO）（2）Fe（SCH_2CON-HCH_3）_2]（2）的IR v（NO）带出现在1751、1700 cm（1）处。在配合物2中，通过N-H伸缩频率为3334 cm（1）（CDCl 3）的IR光谱观察证实了分子内[NH中心点中心点中心点S]氢键的存在，随后通过单晶X射线衍射证实了N-S距离为2.94埃。配合物2在水溶液中的EPR谱为菱形，g（1）= 2.039，g（2）= 2.031，g（3）= 2.013。配合物2和3在暴露于光时快速释放NO。在极性较小的溶剂中，2的光解反应所需时间比3快两倍。2和3在THF中的光化性的代表性时间过程显示NO-脱能力：2 > 3。(C)2008年爱思唯尔B。V.保留所有权利。
HSCH2CONHCH3 and HSCH2CON(CH3)(2) containing a peptide bond are prepared for the synthesis of DNICs with/without intra-molecular hydrogen bonding, respectively. The IR v(NO) bands of [(NO)(2)Fe(SCH2CON-HCH3) 2] (2) appears at 1751, 1700 cm (1). In complex 2, the presence of intramolecular [NH center dot center dot center dot S] hydrogen bonding was verified by the observation of IR spectroscopy with N-H stretching frequency 3334 cm (1) (CDCl3) and subsequently confirmed by single-crystal X-ray diffraction showing N-S distance of 2.94 angstrom. Complex 2 displays the rhombic EPR spectrum with g(1) = 2.039, g(2) = 2.031 and g(3) = 2.013 at in frozen H2O. Complexes 2 and 3 rapidly release NO when exposed to light. The time needed for photolysis reactions of 2 is two times faster than that of 3 in less polar solvent. Representative time courses for the photolability of 2 and 3 in THF display the NO-off ability: 2 > 3. (C) 2008 Elsevier B. V. All rights reserved.