室温和低热固相反应在合成化学中的应用

介绍了室温和低热固相反应的监测手段和影响因素。总结了它在金属原子簇化合物、多酸、简单配位化合物、亚稳态化合物合成以及材料化学和生产实际中的应用。     

配合物形成的三维超分子体系—[Ni(C_6H_4O_2N)_2(H_2O)_4]的水热法合成、晶体结构及热分析

采用水热法用Ni(NO3)26H2O和异烟酸制备出了一种新的由配合物形成的三维超分子体系—[Ni(C6H4O2N)2(H2O)4],并通过X射线衍射对其晶体结构进行了测定。 该晶体属三斜晶系,空间群为Pī, 所得晶胞参数为: a = 6.9228(4), b = 9.6664(19),c = 6.322(1) , a = 96.86(3), b = 113.33(3), g = 110.35(3)°, V = 347.6(1) 3, Z = 1, Mr = 374.98, Dc = 1.791 g/cm3, F(000) = 194, m = 1.443 mm-1。用1362个可观察的 (I > 2s(I))衍射点,修正123个结构参数, 最终偏离因子R = 0.0444,wR = 0.1271。在组成该化合物的基本结构单元[Ni(C6H4O2N)2(H2O)4]中,Ni处于1个稍微拉长的八面体的中心; 各个结构单元之间通过氢键OH…O相互连接,形成了无限伸展的具有层状结构的三维超分子体系。 另外,从差热及热重曲线可以看出,该化合物加热到154 ℃时开始分解, 首先失去4个H2O,再失去2个异烟酸根,最后残余物为NiO。     

几种双核簇合物的EPR谱

本文报导了四个双铜,四个双钼簇合物的EPR谱。这些谱可分成两类:一种类似于单核化合物的EPR谱,谱参数与单核谱相近,但谱强度较单核谱弱,文中称之为“碎片型”;另一类的谱参数与双核偶合的体系相同,谱的强度与双核偶合程度有关、反映双核偶合成簇的性质,称之为“簇型”。两类谱受温度和溶剂的影响分别呈现正常与反常的顺磁性。本文对它们与簇合物结构-性质间的关系作了初步探讨。     

[η~5-Bz_5C_5(CO)_nM]_2的合成及结构

本文通过η~5-Bz_5C_5MNa与氧化偶联试剂Fe_2(SO_4)_3/HOAc/H_2O的反应合成了含η~5-五苄基环戊二烯基配体的两个金属-金属单键化合物[η~5-Bz_5C_5(CO)_3M]_2(1:M=Mo;2:M=W),产率分别为45％和19％。1在沸腾的甲苯中可进一步脱羰而以98％的产率生成金属-金属三键化合物[η~5-Bz_5C_5(CO)_2Mo]_2(3)。1～3的结构均经碳氢分析,IR,~1H NMR和MS鉴定。3的结构尚被单晶X射线衍射分析确证。该晶体属单斜晶系,空间群P2_1/c,晶体学数据:。α=1.1335(5),b=1.3823(4),c=2.1655(6)nm;β=102.33(3)°;V=3.315(2)nm~3;Z=2;D_x=1.34g/cm~3;F(000)=1380。     

一个二维梯状化合物[Ni(μ1，5-dca)2(en)]n的合成，结构和磁性(英)

A new nickel(Ⅱ)-dicyanamide compound, [Ni(dca)₂(en)]_n (1) (dca=dicyanamide anion, [N(CN)₂]^-); en=ethylene diamine), has been synthesized and its structure has been determined by single crystal X-ray diffraction analysis. The crystal is monoclinic, space group P2₁/n with unit cell dimensions: a=0.694 3(1) nm, b=1.041 5(2) nm, c=1.4132(2) nm, and β=90.381°, Z=4, V=1.011 0(3) nm³. In this compound, the adjacent nickel atoms are connected by dca all in μ_1，5-bridging mode to form ladder-like units, which are linked with double dca bridges to generate a regular infinite stair-like structure. Temperature-dependent magnetic susceptibility was also characterized for this compound. CCDC: 208276.     

Structure and electronic transport properties of the Misfit layer compound (LaSe)1.14(NbSe2)2, „LaNb2Se5”︁

The new misfit layer compound (LaSe)_1.14(NbSe₂)₂ has been synthesized from the elements at 1050- and its structure has been determined by a composite approach. The structure has an alternating stacking sequence of [LaSe] and two [NbSe₂] layers along the c direction. The misfit of the two different layers is occurring along the a direction: a₁(LaSe)=6.0191 Å and a₂(NbSe₂)=3.4372 Å therefore yielding a ratio of 1.751 which is very close to 7/4. An investigation of electrical resistivity was done. The crystal shows superconducting properties at 5.3 K.     

希土烯丙基化合物的合成——Ⅱ.镥、钆的烯丙基化合物的合成

本文合成了两个新的对空气极敏感的希土烯丙基化合物,由无水希土氯化物与希丙基锂在四氢呋喃—乙醚中反应制得。产物经元素分析、红外光谱等确定其组成为:Li₂Ln(C₃H₅)₅·3Dioxane(Ln=Gd,Lu)。     

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?     

Synthesis,Structure and Photoluminescence of Co-crystal of Bis[2-(benz(oxa/imida)zol-2-yl)phenolato-κ2N,O]zinc(Ⅱ) Being Site Occupancy Disorder with a Heteroatom Ratio of NH to O (0.408/0.592)

The zinc(Ⅱ) complex with Hpbx (Hpbx = 2-(benzoxazol-2-yl)phenol) and Hpbm (Hpbm=2-(benzimidazol-2-yl)phenol),namely[Zn(pbm)2]1.633[Zn(bpx)2]2.367·DMF·2H2O1,has been synthesized and characterized by X-ray crystallography,FTIR and elemental analysis.The coordination structures are statistically disordered and can be regarded as a co-crystal of [Zn(pbm)2]and [Zn(pbx)2] with the ratio of ca.0.408/0.592.Solvate water and DMF molecules are also present in the lattice.Crystal data for 1:monoclinic,space group P21/c,Mr= 2049.02,Z = 2,α = 9,7571(6),b = 25.6415(16),c = 19.8675(10)(A),β = 111.342(2)°,V = 4629.7(5) (A)3,Dc = 1.470 g/cm3,μ =1.100 mm-1,F(000) = 2104,R = 0.0575 and wR = 0.1282 for 5528 observed reflections (I＞ 2σ(I)).The photoluminescent spectra for this compound have also been studied.     

合成重要中间体1,4位官能化化合物的简便方法

5,6-取代环烯醚2在乙腈的单重态氧反应有效的生成一系列1,4位官能化化合物3。1,4位官能化化合物为合成上重要的中间体。环烯醚2可以通过β-二酰基化合物1和1,3-二溴丙烷在稀碱(碳酸钾/丙酮)条件下缩合生成。