3d夹心化合物的电子结构

用EHMO方法研究了3d环戊二烯夹心化合物的电子结构。结果表明环戊二烯配位体和过渡金属的化学键,Cp-M,含有σ、π和δ三种键型。以π给予键为主,σ和δ键主要是金属轨道的贡献。讨论了这三种键型对3d过渡金属环戊二烯夹心化合物稳定性的影响。     

(R)-N-酰基四氢噻唑-2-硫酮-4-羧酸在DCC存在下与胺的反应

由Ｎ－乙酰四氢噻唑－２－硫酮－４－羧酸（［α］２０Ｄ－１０９．８３°），及Ｎ－苯甲酰四氢噻唑－２－硫酮－４－羧酸（［α］２０Ｄ－１１２．２２°），在Ｎ，Ｎ′－二环己基二亚胺（ＤＣＣ）存在下分别与环己胺、苯胺反应得到光学活性产物（Ｒ）－Ｎ－乙酰四氢噻唑－２－硫酮－４－甲酰环己胺（［α］１７Ｄ－７４．５°），及（Ｒ）－Ｎ－苯甲酰四氢噻唑－２－硫酮－４－甲酰苯胺（［α］１９Ｄ－７．０４°）。用量子化学ＰＭ３方法研究了反应物和产物的电子结构。     

R-四氢噻唑-2-硫酮-4-羧酸二聚反应的量子化学研究

R-四氢噻唑-2-硫酮-4-羧酸反应得到有光学活性的二聚体酰胺双四氢噻唑-2-硫酮并二氧代氢化吡嗪,用半经验量子化学PM3方法研究了反应物、中间产物和二聚体的电子结构.     

R—四氢噻唑—2—硫酮—4—羧酸同R.S—氨基醇的手性识别反应

Ｒ－四氢噻唑－２－硫酮－４－羧酸同Ｒ．Ｓ－亮氨醇、Ｒ．Ｓ－蛋氨醇、Ｒ．Ｓ－苯丙氨醇和Ｒ．Ｓ－色氨醇反应分别得到光学活性非对映体过剩的铵盐；Ｒ－四氢噻唑－２－硫酮－４－羧酸．Ｓ－色氨醇，同时分离出光学活性对映体过剩的Ｒ－亮氨醇，Ｓ－氨蛋醇，Ｓ－苯丙氨醇及Ｒ－色氨醇，用半经验的量子化学ＰＭ３方法研究了氨基醇的最优构型和电子结构，得到了铵盐的最优几何构型。     

SYNTHESIS,STRUCTURE,PROPERTIES AND QUANTUM-CHEMICAL STUDIES OF CUBANE-LIKE CLUSTER COMPOUND WITH ALL-CHELATING LIGANDS [(C_2H_5)_4N]_2{Fe_4S_4[S_2CN(C_2H_5)_2]_4}

Under anaerobic and water-free condition and pure dinitrogen atmosphere, the title com-pound has been synthesized from FeCl_2, (NH_4)_2WS_4, NaS_2CN(C_2H_5)_2 and (C_2H_5)_4NBr. Thecompound crystallizes in the monoclinic space group Cc with cell constants a = 22. 125(6)A,b = 11.313(3) A, c = 25.053(8) A, β= 118.05(2)°, V = 5534.2A~3, Z = 4. It contains cubane-like Fe_4S_4 core. Each Fe atom in the compound is coordinated by a disulfide-chelate ligand.The determination results of the Mossbauer spectrum arid XPS, and quantum-chemical cal-culation all show that the compound contains two kinds of Fe in different valence states butin an equal amount. The scheme of the formation reaction for the compound is given. Thespectra of IR and UV-vis, and redox properties for the compound are reported.