Synthesis of homoleptic Re(I) complexes of isocyano-carboranes and the X-ray structure of hexakis(p-carboran-1-yl-isonitrile)Re(I)

Two homoleptic Re(I) complexes of ortho and para-carborane isocyanide ligands were prepared as the first examples of a new class of metal-based BNCT and BNCS agents. The target compounds were prepared in low yield through the reaction of [Re₂(O₂CPh)₄Cl₂] and [Re₂(OAc)₄Cl₂] with 3-isocyano-1,2-dicarba-closo-dodecaborane and a para-carborane azetidine derivative respectively. The desired product from the latter reaction was characterized crystallographically and is only the second reported molecular structure of a homoleptic Re(I) isonitrile complex.     

[Co(amp)2Cl2]2[ZnCl4]体系中两对称异构体的2D NMR研究

The two symmetrical isomers in [Co(amp)₂Cl₂]₂[ZnCl₄](amp=2-(Aminomethyl)pyridine) system were syn-thesized by general oxidation method and were separated by chromatography and recrystallization method. Their configurations were assigned by using 2D NMR techniques, particularly the NOESY NMR spectra. Solvent used was Me₂SO-d₆ with the central peak of the CD₃ septet as the reference ( ₁₃C,δ 39.37; ₁H,δ 2.49 relative to SiMe₄). Cation exchange media used was Dowex 50Wx 2(H⁺ form, 200～400mesh; Biorad).     

三维聚合物双(三丁基锡)戊二酸酯的合成及晶体结构研究

用三丁基氯化锡与戊二羧酸二钠以2:1摩尔比反应,合成了双（三丁基锡）戊二羧酸酯,并用元素分析、红外光谱、核磁共振氢谱及X-射线单晶衍射进行了表征和结构测定。X-射线单晶衍射法测定表明,化合物属单斜晶系,空间群为Cc,晶胞参数:a=13.984（3）,b=16.164（3）,c=16.894（3）A,β=107.457（3）°,V=3642.9（11）A3,Z=4,C29H60O4Sn2,Dc=1.251g/cm3,μ=1.394 mm-1,R=0.0500,wR=0.0874,F（000）=1416。晶体结构中存在2种化学环境不同的三角双锥构型的锡原子,由于配体中2个羧基在不同方向的交联作用,使化合物呈现三维立体骨架结构,并且在骨架结构中存在沿a、b、c轴3个方向伸展的规则的大环直孔道。     

Simultaneous comparison of δ31P and 1JPN for the assignment of E/Z-stereochemistry of the phosphorus-nitrogen double bond in iminophosphines R-P=N-R′

 The analysis of ³¹P and ¹⁵N NMR data of a series of 40 iminophosphines R-P=N-R′ reveals that the E/Z-stereochemistry of the PN double bond can be predicted on the basis of a simultaneous comparison of the values of δ³¹P and ¹J_PN. Received: 31 May 1996/Revised: 2 July 1996/Accepted: 5 July 1996     

轻希土硫氰酸盐与2, 3, 11, 12, -四苯基-1, 4, 7, 10, 13, 16-六氧-2, 11-十八环二烯配合物的合成及XPS研究

合成了六种轻希土硫氰酸盐与标题不饱和冠醚的新固体配合物,进行了元素分析,摩尔电导率、DTA、UV、IR和XPS等表征.对Ln(NCS)₃·L和Ln(NCS)₃的XPS研究中,得到它们组成原子芯能级电子(Ln3d_5/2,Ols,Nls,S2p)的结合能信息;观察到除Y3d_5/2外Ln3d_5/2(Ln=La、Ce、Pr、Nd、和Sm)的伴峰结构,Ln3d_5/2结合能与原子序数呈线性关系,并推断类似化合物Pm³d_5/2结合能在1035eV附近.     

正丁基锂四氢呋喃引发α-甲基苯乙烯阴离子平衡聚合动力学及反应机理研究

本文研究了以正丁基锂为引发剂,四氢呋喃为添加剂,环己烷为溶剂中的α-甲基苯乙烯阴离子平衡聚合动力学。讨论了体系中的反应活性种;提出了聚合机理;得到了聚合温度为20℃时的平衡单体浓度与活性种速率常数及添加剂浓度之间的关系式。     

一种新型联萘基旋光共轭聚合物的圆二色谱和圆偏振荧光光谱

众所周知 ,聚合物的光电性质依赖于聚合物链的构象和 (或 )组成 ,通过在聚合物上引入手性单元 ,采用圆二色谱 ( CD)和圆偏振荧光光谱 ( CPL)等方法可表征聚合物结构 [1] .近年来 ,由于圆偏振光可用作光数据存储和液晶显示器背景光 [2 ] ,人们开始注重共轭聚合物圆偏振光材料的研究 .共轭聚合物的光致和电致圆偏振光的现象由一种带手性侧链的聚噻吩[3 ] 和一种带手性侧链的聚 (对苯撑乙烯 ) [4 ]产生 ,但它们的圆偏振荧光度 (用不对称因子 glum=2 ( IL-IR) / ( IL+IR)表示 ,IL 和 IR 分别指左圆偏振光强度和右圆偏振光强度 )相对较低 …     

4-[2-(4,6-二甲氧基-2-嘧啶氧基)苄胺基]苯甲酸正丙酯的合成和晶体结构

2-甲砜基-4,6二甲氧基嘧啶和N-(4-丙氧羰基苯基)-2-羟基苄胺在四氢呋喃溶液中反应, 生成标题化合物4-[2-(4,6-二甲氧基-2-嘧啶氧基)苄胺基]苯甲酸正丙酯,并测定了其晶体结构。该化合物分子式为C23H25N3O5,晶体属单斜晶系,空间群为P2/n,晶胞参数为a = 14.8504(8),b = 9.4420(4),c = 16.3129(9) 牛 = 104.881(1)埃琕 = 2210.6(2) 3,Z = 4,Dc = 1.272 g/cm3,F(000) = 896.00,(MoK? = 0.91 cm-1,R = 0.051,wR = 0.118,获得19761衍射数据,其中独立衍射点5004个。经元素分析、IR、MS和HNMR等对化合物的结构进行了表征。在分子结构中,各有3个不同的共轭平面。嘧啶环和苯环(C(7) C(12)),及苯环(C(14) C(19))的夹角分别为99.18 , 164.15埃?个苯环之间的夹角为94.93啊;衔锍世啻焦瓜蟆?