Half-sandwich 1,3-Di-t-butylcyclopentadienyl Rhodium Complexes Containing Sulfido Ligands
KONG Qing-An, JIN Guo-Xin
Treatment of 1,3-di-t-butylcyclopentadiene with rhodium trichloride in EtOH leads to the formation of binuclear half-sandwich complex [Cpt RhCl(_-Cl)]2 (1) (Cpt=Z5-tBu2C5H3) which reacts with trimethylphosphine to give Cpt Rh(PMe3)Cl2 (2) in high yield. 2 reacts with ammonium polysulfide, (NH4)2Sx to give cyclooligosulfido half-sandwich complexes Cpt Rh(PMe3)(Sn)(n=4(4a),6(4b)). Desulfurization of 4b by excess PPh3 results in cyclotetrasulfido product 4a, while 4a takes up sulfur from polysulfide to convert cyclohexasulfido product 4b. The reaction of 2 with Et4NI gives diiodide complex 3 which is determined by single crystal X-ray crystallographic analysis.
关键词: half-sandwich complex, rhodium, sulfur, desulfurization, metalla cyclo-oligosulfide, X-ray crystal structure
牛红艳, 胡正利, 应佚伦, 龙亿涛
【化学学报】doi: 10.6023/A19060230
环二腺苷酸(c-di-AMP)是原核细胞中普遍存在的第二信使,不仅能够有效调控细胞生长、离子转运、细胞壁代谢平衡等多种生理过程,还能引发I型干扰素应答,激发机体天然免疫反应.本实验使用单个气单胞菌溶素(Aerolysin)纳米孔道蛋白构建的单分子界面,对c-di-AMP进行单分子测量研究.为提高Aerolysin纳米孔对带负电小分子化合物的测量灵敏度,本实验利用LiCl为支持电解质,有效屏蔽Aerolysin孔口表面负电荷,减小c-di-AMP与Aerolysin纳米孔之间的静电排斥,从而显著增强了Aerolysin纳米孔道对单个c-di-AMP分子的检测能力.实验结果显示,在90 mV电压下,每分钟在LiCl中获得的有效穿孔事件的数量最高可达同条件KCl支持电解质的30倍,且有效穿孔事件占总体事件的比例在不同电压下提升了7~11倍.进一步表明,使用LiCl支持电解质,可有效增强Aerolysin孔道对带负电小分子化合物的测量灵敏度.因此,本研究实现了Aerolysin纳米孔道对单个环二核苷酸的高灵敏免标记检测,有望为单分子水平上阐明新型免疫干扰机制提供新的分析方法.
关键词: 环二腺苷酸, 环二核苷酸, 气单胞菌溶素, 单分子界面, 生物纳米孔道
Preparation, Structures and Thermal Stabilities of Four Transition Metal Complexes Constructed by 3, 7-Di(3-pyridyl)-1, 5-dioxa-3, 7-diazacyclooctane Bipyridine Ligand
【无机化学学报】doi: 10.11862/CJIC.2021.009
Four transition metal complexes, [Co(NO3) (H2O)2(L)2]NO3 (1), [Co2Cl4(L)2] ·CH2Cl2 (2), [Cd2(AcO)4(L)2] ·4CH3OH (3) and[Cd2(NO3)2(CH3OH)2(H2O)2(L)2](NO3)2·2H2O (4), were synthesized by employing a clamplike bipyridine ligand 3, 7-di(3-pyridyl)-1, 5-dioxa-3, 7-diazacyclooctane (L). Single-crystal X-ray analysis reveals that complex 1 is mononuclear structure; 2 is macrocyclic dimer; wheras 3 and 4 are rectangular dinuclear structures. The ligand molecules in these complexes has shown three types of coordination mode including mono-dentate, trans-bridge and cis-bridge. All of the complexes were also characterized by elemental analysis, IR, thermal stabilities and singlecrystal structure analysis.CCDC: 940778, 1; 915840, 2; 1446573, 3; 1446574, 4.
关键词: cobalt, cadmium, 3, 7-di(3-pyridyl)-1, 5-dioxa-3, 7-diazacyclooctane, bipyridine, crystal structure