氯代膦烯化合物与零价钯的氧化加成反应机理探讨

与氯代烯烃或芳烃相反, 氯代膦烯与零价钯的氧化加成反应可以在温和条件下进行. 提出了可能的反应机理. 起始卤代膦烯的结构决定了反应历程和最终产物的结构.     

含松香骨架的新型手性季铵盐相转移催化剂的合成及其在不对称环氧化反应中的应用

以天然松香为原料合成了4个新型手性季铵盐类相转移催化剂, 并用于催化不对称查尔酮环氧化反应, 发现这类手性相转移催化剂可以有效地催化查尔酮的不对称环氧化, 环氧化产物ee最高达20%.     

ON A SUFFICIENT CONDITION FOR THE METRIC COEFFICIENTS TO BE CONFORMALLY TIME-INDEPENDENT

The statement in Rindler's book "Essential Relativity" [(Springer-Verlag, New York, 1977), p. 119] claiming that "the metric coefficients are time-independent if light signals tracing out the same path always take the same coordinate time" has two problems, the first one has been pointed out by us in a recent paper "relation between choosing ‘good' coordinates and the behavior of light signals" [Acta Physica Sinica (Overseas Edition), 3(1994), 881], while the second is the main focus of the present article.     

High-Valent Manganese in Polyoxotungstates. 3. Dimanganese Complexes of gamma-Keggin Anions

Dimanganese-substituted gamma-Keggin heteropoly tungstates have been synthesized by reaction of the lacunary species gamma-[(SiO(4))W(10)O(32)](8)(-) with appropriate mixtures of Mn(II) and MnO(4)(-). The crystal structure of [(CH(3))(3)(C(6)H(5))N](4)[(SiO(4))W(10)Mn(III)(2)O(36)H(6)].2CH(3)CN.H(2)O (anion 1) was determined by X-ray diffraction. Crystallographic data: space group P&onemacr;, a = 12.951(3) ?, b = 14.429(3) ?, c = 20.347(4) ?, alpha = 81.95(3) degrees, beta = 88.92(3) degrees, gamma = 67.48(3) degrees, V = 3475.2(13) ?(3), and Z = 2. The final R value is 7.29% for 15861 reflections with I > 2sigma(I). The anion has the anticipated gamma-Keggin structure with virtual C(2)(v)() symmetry. The two Mn cations occupy adjacent, edge-shared octahedra with bridging hydroxo and terminal aqua ligands. Anion 1 can be oxidized and reduced to the corresponding Mn(III)Mn(IV) (2) and Mn(II)(2) (3) species respectively. The magnetic susceptibility of 1 between 2 and 300 K indicates that the Mn(III) cations are antiferromagnetically coupled, with J = -17.0 cm(-)(1) and g = 1.965. No simple magnetic behavior was observed for 2 or 3.     

Yb(C~6Me~6) (AlCl~4)~3·MeC~6H~5 的合成及其晶体结构

合成了一种新的芳烃络合物Yb(C~6Me~6)(AlCl~4)~3·MeC~6H~5 , 并确定了其晶体结构.     

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。     

超分子化合物[M(4,4''''-bipy)2(H2O)4]·(4,4''''-bipy)2·(3,5-diaba)2·8H2O](M=Co,Ni,Cd)的合成及晶体结构

合成了3个超分子化合物[M(4,4'-bipy)2(H2O)4]·(4,4'-bipy)2·(3,5-diaba)2·8H2O(M=Co(1),Ni(2),Cd(3);4,4'-bipy=4,4'-联吡啶;3,5-diaba=3,5-二氨基苯甲酸阴离子),用红外光谱、元素分析及X-射线单晶衍射进行了表征。3个化合物的晶体都属于单斜晶系,空间群为P2/c。晶体学参数:化合物1:a=0.9389(2)nm,b=0.7751(1)nm,c=3.9284(6)nm,β=90.14(2)°,V=2.85880(69)nm3,Z=4,Dc=1.397g·cm-3,F(000)=1266,μ=0.380mm-1,R1=0.0349,wR2=0.0829;化合物2:a=0.9383(2)nm,b=0.7753(1)nm,c=3.9218(6)nm,β=90.09(1)°,V=2.85280(68)nm3,Z=2,Dc=1.399g·cm-3,F(000)=1268,μ=0.420mm-1,R1=0.0366,wR2=0.0805;化合物3:a=0.94091(13)nm,b=0.77885(11)nm,c=3.9712(5)nm,β=90.10°,V=2.9102(7)nm3,Z=2,Dc=1.433g·cm-3,F(000)=1308,μ=0.454mm-1,R1=0.0468,wR2=0.0964。3,5-diaba未参与配位,在配位阳离子[M(4,4'-bipy)2(H2O)4]2 中,金属离子M髤与来自2个4,4'-bipy的2个氮原子和4个水分子的氧原子配位,呈八面体的几何构型。分子中还存在未配位的4,4'-bipy。通过配位阳离子、游离4,4'-bipy及未配位的3,5-diaba间的丰富氢键,构建成具有三维结构的超分子化合物。     

对甲苯磺酰谷氨酸桥联的一维双链锰配合物的合成、表征与晶体结构

A one-dimensional double-chain coordination polymer [Mn(phen)(tsgluo)] was synthesized in a mixed solution and its crystal structure was determined by X-ray diffraction method. It crystallizes in orthorhombic system with space group P2₁2₁2₁. The crystal data are: a=0.530 78(17) nm, b=1.723 9(5) nm, c=2.456 9(8) nm, Z=4, μ=0.729 mm^-1, D_c=1.579 g·cm^-3, V=2.248 1(12) nm³, R₁=0.033 1, ωR₂=0.078 9. In the title complex, each Mn(Ⅱ) ion presents a octahedral geometry with the coordination of two nitrogen atoms from 1,10-phenanthroline and four oxygen atoms from three different tsgluo^2- ligands. The γ-carboxyl coordinates to Mn(Ⅱ) in the mode of bidentate chelate, while the α-carboxyl coordinates in a bidentate bridging mode. CCDC: 253910.     

α-硝基环烷酮的制备及其合成应用

介绍了α-硝基环烷酮的制备方法, 以及它们的特殊反应性和合成应用, 参考文献40多篇.     

双环[2，2，1]庚-5-烯-2-甲酰基芳香醛腙的合成和生物活性

合成了七个未见文献报道的双环[2，2，1]庚-5-烯-2-甲酰基芳香醛腙席夫碱 类化合物。用核磁共振氢谱、红外光谱和元素分析对新化合物进行了表征，考察了 它们的生物活性。结果表明某些化合物具有除草作用、抗菌作用和植物生长调节作 用。