综合化学新实验——手性席夫碱Ni(Ⅱ)络合物的合成与表征

本实验属于化学系综合化学实验,其构思来自手性络合物的立体选择性合成。学生可通过本实验从实践和理论上探讨手性配体在立体选择性合成手性络合物中的作用并掌握对手性络合物组成和结构的各种表征方法特别是CD光谱方法

Study on Solid-State Circular Dichroism Spectroscopy and Its Application to Chiral M(II) Schiff Base Complexes

结合课题组近期的相关研究,对固体CD光谱在手性配合物研究中的应用,特别是手性样品固体CD光谱的测试方法进行了概述,通过对四对手性席夫碱M(II)(M=Ni、Cu)配合物的固体和溶液CD光谱进行比较研究,发现配合物的手性构型在固液相中保持一致,但其固液CD光谱之间存在不同程度的差异,可能是由于相应配合物在固体和溶液相中的四面体扭曲或构象的微妙不同所致.An account on the application of solid-state CD on chiral metal complexes is briefly reviewed. Special focus is on the methods to record solid-state CD spectra of chiral solid sample, and then we switch to the comparison between solid-state and solution CD spectra of four pairs of chiral M(II) (M = Ni, Cu) Schiff base complexes. The solid-state CD spectra reveal that the chiral complexes mantain the same handeness found in solution states. But it is notable that there are some differences between the solid-state and solution CD spectra for the selective chiral complexes, which may be ascribed to some subtle tetrahedral distortion or conformational distinctions of the complexes between the two states.国家自然科学基金(20171037);; 南京大学配位化学国家重点实验室基金;; 厦门大学科技创新项目(B类,2003XDYY39)资

低品位萤石湿法制氟硅酸钠

在60℃温度下,用30%硫酸与二氧化硅作用于含氟化钙85%的低品位萤石矿,反应持续1小时半,在氯化钠过量的条件下第一次沉淀可得到合格品氟硅酸钠的产率达75%以上,经后处理可使产率提高至90%

Study on solid-state circular dichroism spectroscopy and its application to chiral M(II) Schiff base complexes

An account on the application of solid-state CD on chiral metal complexes is briefly reviewed. Special focus is on the methods to record solid-state CD spectra of chiral solid sample, and then we switch to the comparison between solid-state and solution CD spectra of four pairs of chiral M(II) (M = Ni, Cu) Schiff base complexes. The solid-state CD spectra reveal that the chiral complexes maintain the same handeness found in solution states. But it is notable that there are some differences between the solid-state and solution CD spectra for the selective chiral complexes, which may be ascribed to some subtle tetrahedral distortion or conformational distinctions of the complexes between the two states

Synthesis and Characterization of Novel Chiral Mo(0) Complexeswith Chiral Pineno-bipyridine Ligands

为了探讨含手性蒎烯基联吡啶的手性钼(0)络合物的结构对光谱(特别是CD光谱)性质的影响,合成了两个新型手性钼络合物(+)CD452[Mo(CO)4(LRR)]和[Mo(CO)4(LSS)].用元素分析、IR、UV vis、CD、1HNMR和13CNMR等对其进行了充分表征.研究结果表明:两种络合物为一对具有几乎完全相同物理化学性质、配体互为对映体的光学异构体;两者在可见区的CD曲线呈现弱Cotton效应,且大致为镜象对称,说明在相应的手性络合物中,由于联吡啶上相反手性的蒎烯基通过中心金属钼对MLCT发色团产生了手性微扰作用,从而产生诱导CD效应.A pair of novel chiral complexes (+)~(CD)_(452)[Mo(CO)_4(L~(RR))] and (-)~(CD)_(452)[Mo(CO)_4(L~(SS))] were prepared and characterized by EA, UV-vis, IR, NMR and CD spectra in order to investigate the influence of structures on the spectral (especially CD) properties of chiral molybgenum(0) complexes with chiral pineno-bipyridines. The results reveal that the two chiral complexes have almost the same physico-chemical properties and they are a pair of optical isomers with the enantiomeric ligands. Their CD spectra in the visible range show weak Cotton effects, which are approximately of mirror image, indicating that the appended pineno-groups with opposite chirality in bipyridines can perturb the MLCT chromophores in the related complexes through the molybgenum centers respectively and lead to induced CD effects.国家自然科学基金(20171037,20073034);; 福建省自然科学基金(2002F016,C0020001)资

Synthesis and characterization of lamellar structural materials Ni2P2S6 by room temperature solid state reaction

Results of XRD and Raman spectra show the successful preparation of lamellar structural materials Ni2P2S6 by a new synthetic route - room temperature solid state reaction, Compared with the traditional high temperature solid state reaction, the preparation method adopted here has the following advantages: fast reaction rate, low energy cost, high homogeneity of final products and the facility of preparation in quantity, Study of TG-DTA shows the final product Ni2P2O7 and the existence of an intermediate metastable Ni2P2O6 phase of Ni3P2S6 thermo-oxidation in air