Mo—Cu—S原子簇化合物（Mo2Cu6S6（SCMe3）2（O）2（PPh3）4）（I）和（MoCu3S3（…

基本标题簇合物的快原子质谱研究，提出该二簇合物在质谱过程中的可能断裂途径及其簇骼转换的相关性。     

Mo－Cu－S原子簇化合物［Mo_2Cu_6S_6（SCMe_3）_2（O）_

基于标题簇合物的快原子质谱研究，提出该二簇合物在质谱过程中的可能断裂途径及其簇骼转换的相关性。     

Mo（W）—Cu（Ag）—S原子簇化合物的反应

总结了Ｍｏ（Ｗ）－Ｃｕ（Ａｇ）－Ｓ原子簇化合物的反应，并把这些反应分成５类：取代反应，加成反应，降价反应，多聚反应和氧化还原反应。从低热固相反应的角度探讨了簇合物反应对合成新原子族化合物的重要性。     

新型六核钼原子簇化合物{[Mo3（μ3—S）（μ—S2）2（dtp）3]—（μ3—S）（η…

［Ｍｏ３（μ３－Ｏ）（μ－Ｓ）３（μ－ＯＡｃ（ｄｔｐ）３（ｐｙ）］和［Ｍｏ３（μ－Ｓ）３（μ－ＯＡｃ（ｄｔｐ）３－（ｐｙ）］（ｄｔｐ＝Ｓ２Ｐ（ＯＣ２Ｈ５）２＾－）族合物分别与金属化合物ＢｉＩ３和ＳｂＢｒ３进行原子簇反应均能获得意外产物｛［Ｍｏ３（μ３－Ｓ）（μ－Ｓ２）２（ｄｔｐ）３］（μ３－Ｓ）（η＾３－Ｓ２）［Ｍｏ２（μ３－Ｓ）（μ－Ｓ）３（μ－ＯＡｃ）（ｄｔｐ）２］｝六核钼簇。其结构实际上是由     

STRUCTURE OF {Mo4S4（μ—OAc）2[S2P（OC2H5）2]4H}

<正> {Mo4S4(μ-OAc)2(dtp)4H}3,(dtp=S2P(OEt)2),Mr=1371.60,Or-thorhombic, space group Pcab, a = 18. 90 (2) ,b = 21. 678 (4 ) , c = 24. 491 (4 ) A , V = 10031(7)A3,Z=8,Dc=1.818g/cm-3,F(000)=5464,λ(MoKa)=0.71073A,finalR= 0. 069 for 3738 independent reflections. This is a successful example of the formation of [Mo4S4]5+ from[3+1] reaction mode. The results of the structure determination indicate that the configuration of the title compound exhibits a tetranuclear cubane-type core [Mo4S4]5+ with six Mo - Mo distances in the range 2. 685~2. 969A and is very similar to that of the previously characterized compound {Mo4S4(μ-OAc)2(dtp)4}2, [Mo4S4]6+, which was obtained directly by the reaction of MoCl3·3H2O with dtp. Some notable differences, however, can be found when six Mo - Mo bond distances and bonding parameters of the four terminal bidentate ligands (dtp) are compared between these two compounds , That can be attributed to the difference in the oxidation state of these two clusters .     

[Mo2FeS8O2][Et4N]3CH3CN原子簇化合物的晶体结构

[Mo_2FeS_8O_2][Et_4N]_3·CH_3CN晶体属三斜晶系,PI空间群.α=9.998(1)A,b=13.868(3)A,c=16.796(3)A,α=74.66(2)°,β=85.41(1)°,ν=72.21(1)°,Ζ=2.结构参数经块矩阵最小二乘法精修后,最后的偏离因子R=0.037,R_w=0.034.平均键长Mo—Fe为2.722A,Mo—S为2.358A,Fe—S为2.244A,Mo—O为1.697A.结果表明:标题化合物是一个结构新颖的原子簇化合物.它是由一个三价原子簇阴离子与三个一价的乙基季铵阳离子靠静电引力结合在一起,又溶剂合一个乙氰分子的原子簇化合物而形成.     

Solid Synthesis and Crystal Structure of Compound [（PPh3）3Cu2MoOS3]

ＳｏｌｉｄＳｙｎｔｈｅｓｉｓａｎｄＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆＣｏｍｐｏｕｎｄ［（ＰＰｈ_３）_３，Ｃｕ_２ＭｏＯＳ_３］ＬｉｎＺｈｅｎ－Ｇｕａｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＦｕｊｉａｎＮｏｒｍａｌＵｎｉｖｅｒｓｉｔｙ，Ｆｕｚ...     

Synthesis,Structural Characterization and Reactivity of Two New Triangular Molybdenum Cluster Compounds：Mo3T37—[S2CN（CH2CH2OH）2]3I and Mo3Te4Y3[S2P（^iPrO）2]3I（Y3=1.43Te＋1.57S）

Two triangular molybdenum‐tellurium clusters, Mo₃Te₇‐[S₂CN (CH₂CH₂OH₂]₃I (1) and Mo₃Te₄Y₃[S₂P(ⁱPrO)₂]₃I (Y₃ = 1. 43Te+ 1.57S) (2), were obtained from the reaction of K · HOdtc [HOdtc = S₂CN(CH₂CH₂OH)₂] or K·ⁱPr₂dtp (ⁱPr₂dtp = S₂P[OCH(CH₃)₂]₂) with a mixed product of elements Mo, Te(S) and I₂ at high temperature. The structures of the two compounds were determined by X‐ray crystallography study. Crystal data are, (1): monoclinic, P2₁/n, a = 1.6256(3), b = 1.3264(2), c = 1.8808(4) nm, β=96.923°, V = 4.025.9 (14) nm³, D_cal = 3.050g·cm‐³, Z = 4, and (2): monoclinic, P2₁/n, a = 1.4564(2), b = 2.3917(4), c = 1.5094(3) nm, β = 114.35(2)°, V = 4.0259(14) nm³, D_cal = 2.449 g·cm^?3 and Z = 4. Single crystal analyses show that 1 consists of discrete Mo₃Te₇[S₂CN(CH₂CH₂OH)₂]₃I connected into three‐dimensional framework via hydrogen bonds, while 2 forms a linear chain via Te(S)—I interaction.     

蝴蝶形原子簇化合物[MoOS3Cu2(PyPPh2)3]的制备、晶体结构 和非线性光学性质 研究

采用固相反应方法以[NH4]2[MoS2O2],CuI.Et4NBr和2-)二苯基膦)吡啶(PyPPh2)为原料制备了标题化合物。其结构用单晶分析法测定。测得化合物的分子式为MoOS3Cu2(PyPPh2)3],该晶体结构属三斜晶系,空间群为P1,所得晶胞参数为a=1.16736(4)nm,b=1.42254(5)nm,c=1.68034(6)nm,α=100.07°,β=103.2450(10)°,γ=105.0650(10)°,V=2.53991(15)nm^3,Z=2,Dc=1.504g·cm^-3,F(000)=1166,μ=13.57cm^-1.偏差因子R1=0.0590,wR2=0.1238。簇合物具有高度弯曲的蝴蝶状核,其中MoOS3^2-基团以三齿配体的形式与两个具有不同构型的Cu原子配位,氧原子不参加配位仅以端基形式存在。通过标题化合物在DMF中非线性光学性质的测定,表明其具有较好的非线性吸收和与以往不同的自散焦效应,算得其非线性吸收系数α2=4.4×10^-11m·W^-1,非线性折射系数n2=—8.225×10^-18m^2·W^-1;从而说明外围配体对非线性光学性质也具有大的影响作用。