对苯二甲酸二丙炔醇酯与C02(CO)8、M02Cp2(CO)4和RuC02(CO)11的反应

室温下,对苯二甲酸二丙炔醇酯分别与Co2(CO)8,Mo2Cp2(CO)4和RuCo2(CO)11反应,得到三个有机金属化合物[C6H4-p-(CO2CH2C2H-μ)2][Co2(CO)6]2(1)、[C6H4-p-(CO2CH2C2H)2][RuCo2(CO)9]2(2)和[(HC2CH2OCO)C6H4-p-(CO2CH2C2H-μ)][Mo2Cp2(CO)4](3).研究发现三种金属核对端炔氢的屏蔽作用依次为RuCo2(CO)9＞Co2(CO)6＞Mo2(CO)4Cp2.化合物1的晶体衍射发现,属三斜晶系,空间群PT,a=8.139(2)A,b=8.808(3)A,c=1 1.343(3)A,β=96.260(6)°,V=773.4(4)A3,Z=1,Dc=1.748g@cm-3,R=0.0513,wR=0.1266.     

{Na2[μ2-(C6H4O2)2](C6H4OOH)2}4-的结构及其在固态合溶液中的NMR比较

The new compound （NH3CH2CH2NH3）2{Na2[μ2-（C6H4O2）2]（C6H4OOH）2} has been synthesized and characterized by elemental analysis, IR, UV, NMR and single crystal X-ray diffraction. The yellow crystals crystallized in the triclinic system with space group P-1 and a=0.6091（2） nm, b= 1.0274（3） nm, c= 1.2466（4） nm, α=89.073（6）°, β=89.376（6）°, γ=78.873（5）°, V=0.7653（4） nm^3, Z= 1, R1=0.0568, wR2=0.1198. Every sodium ion coordinates in trigonal prismatic fashion with two O atoms from a terminal chelating catecholato ligand and four O atoms from bridging P2 catecholato ligands, Two neighboring NaO6 trigonal prisms are face-shared and centrosymmetric with regard to the inversion center consisting of four tri-bridging O atoms to form a binuclear cluster {Na2[μ2-（C6H4O2）2]}^2- anion. The comparison of ^13C NMR spectrum of tlie complex in solid state with that in solution indicated that the rapid exchange between the bridging [μ2-（C6H4O2]^2- and terminal [C6H4OOH]^- ligands was present in solution.     

[Mo(C9H6NO)2O2]的合成和晶体结构

合成了标题化合物[Mo(C9H6NO)2(O)2](C9H6NO=8-羟基喹啉),测定了化合物的晶体结构.晶体属单斜晶系,空间群Cc,a=13.372(3),b=9.421(2),c=13.554(3)A,β=109.71(3)°,V=1607.6(8)A3.结构由直接法解出,最后可靠性因子R=0.0473,Rw=0.062.Mo原子为6配位,位于八面体的中心.两个配体氧相互处于邻位,分别与8-羟基喹啉中的N原子处于对位.     

Reaction of Mo(CO)_6 with Alkoxide: Synthesis and Structure of the Mo(0)-OR Complex [Et_4N]_3[Mo_2(CO)_6(μ-OC_6H_4OCH_2C_6H_5)_3]

The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo(0) compound [Et4N]3[Mo2(CO)6(μ-OC6H4OCH2- C6H5)3] 1. 1 crystallizes in monoclinic, space group P21/c with a = 15.359(2), b = 18.378(3), c = 24.952(2), β = 102.268(4)°, V = 6882.3(16) 3, Mr = 1348.34, Z = 4, Dc = 1.301 g/cm3, F(000) = 2832 and μ = 0.424 mm-1. The final R = 0.0606 and wR = 0.1552 for 9396 observed reflections (I > 2σ(I)). 1 contains a [Mo2O3]3- core in triangular bi-pyramidal configuration and each Mo atom adopts a distorted octahedral geometry with three carbon atoms from carbonyls and three μ-O atoms from C6H5CH2OC6H4O- bridging ligands. The Mo…Mo distance is 3.30(8) , indicating no metal- metal bonding. A formation pathway via forming a di-molybdenum(0) di-bridging OR compound [Mo2(μ-OR)2(CO)8]2- has been figured out and the reaction of Mo(CO)6 with alkoxide has also been discussed.     

[Cp2Ln(m-h1:h2-OC(SR)=CPh2 )]2 的合成和表征

[Cp2Ln（μ-SR）]2 was reacted with Ph2C=C=O to yield ketene mono-insertion products [Cp2Ln（μ-η1：η2-OC（SR）=CPh2）]2 [R=Bn, Ln=Yb （1）, Er （2）, Y （3） and R--Ph, Ln=Yb （4）], indicating that the reactions of organolanthanide thiolates with ketenes are independent of the nature of the thiolate ligand and the ketene as well as the reaction condition. These reactions could provide an efficient method for the synthesis of organolanthanide complexes with the a-thiolate-substituted enolate ligand. All these complexes were characterized by elemental analysis and spectroscopic properties and the structure of complex 1 was determined through X-ray single crystal diffraction analysis.     

Synthesis and Crystal Structure of Cluster [C6H4-1,2-(CO2CH2C2H-μ)2][Co2(CO)6]2

The reaction of dipropargyl phthalate C6H4-1,2-(CO2CH2C2H-μ)2 1 with octacarbonyldicobalt 2 resulted in the formation of red complex [C6H4-1,2-(CO2CH2C2H-μ)2][Co2(CO)6]2 3, in which each Co2(CO)6 group coordinates to one of the two C≡C bonds of 1. Molecular structure of complex 3 was determined by single crystal X-ray analyses. The crystal belongs to the monoclinic system, space group P21/a with the following crystallographic parameters: a=8.521(2), b=29.143(6), c=12.918(7)(A), β= 100.12(3)°, V=3158(2)(A)3, Z=4, Mr=814.09, Dc=1.712 g.cm-3, F(000)=1608, μ(Mo-Kα)=21.37 cm-1 and final R=0.044 for 3151 observations.     

Synthesis and Characterization of Tetrametal Cluster [Co2(CO)6][μ-HC2CH2OCH2C2H-μ][Co2(CO)6]

The treatment of dipropargyl ether HC2CH2OCH2C2H with Co2(CO)8 resulted in the formation of a novel cluster [Co2(CO)6][μ-HC2CH2OCH2C2H-μ][Co2(CO)6]. The cluster was characterized by C/H analyses, IR and 1H NMR spectroscopy and X-ray crystal structure determination. It belongs to monoclinic system, space group P21/c with the following crystallographic parameters: a=18.149(2), b=7.0111(7), c=20.897(2)(A), β=115.318(7)°, V=2403.7(5)(A)3, Z=4, Mr=665.97, Dc=1.840 g·cm-3, F(000)=1304.00, μ(Mo-Kα)=27.76 cm-1 and R=0.030 for 2372 observed reflections.     

Reaction of Mo(CO)6 with Alkoxide: Synthesis and Structure of the Mo(0)-OR Complex [Et4N]3[Mo2(CO)6(μ-OC6H4OCH2C6H5)3]

The reaction of molybdenum hexacarbonyl with C6H5CH2OC6H4ONa and Et4NBr in CH3CN at 60 ℃ afforded the di-nuclear Mo(0) compound [Et4N]3[Mo2(CO)6(μ-OC6H4OCH2- C6H5)3] 1. 1 crystallizes in monoclinic, space group P21/c with a=15.359(2), b=18.378(3), c=24.952(2)(A), β=102.268(4)°, V=6882.3(16) (A)3, Mr=1348.34, Z=4, Dc=1.301 g/cm3, F(000)=2832 and μ= 0.424 mm-1. The final R=0.0606 and wR=0.1552 for 9396 observed reflections (Ⅰ ＞ 2σ(Ⅰ)). 1 contains a [Mo2O3]3- core in triangular bi-pyramidal configuration and each Mo atom adopts a distorted octahedral geometry with three carbon atoms from carbonyls and three μ-O atoms from C6H5CH2OC6H4O- bridging ligands. The Mo…Mo distance is 3.30(8) (A), indicating no metalmetal bonding. A formation pathway via forming a di-molybdenum(0) di-bridging OR compound [Mo2(μ-OR)2(CO)8]2- has been figured out and the reaction of Mo(CO)6 with alkoxide has also been discussed.     

Cu/MoO3-TiO2光催化CO2与C3H6反应合成甲基丙烯酸的性能

 研究了Cu/MoO3-TiO2上CO2和C3H6的吸附特性及其光催化CO2与C3H6反应合成甲基丙烯酸(MAA)的性能. 结果表明,在Cu/MoO3-TiO2催化剂表面存在金属Cu位、Lewis酸位Mo6+和Ti4+以及Lewis碱位Mo-O-Ti的桥氧和Mo=O的端氧三类活性中心. 在金属Cu位和Lewis酸位Ti4+(Mo6+)的协同作用下,CO2形成活性较高的卧式吸附态Cu-(CO)-O→Ti4+(Mo6+),C3H6的β-H和β-C分别吸附在Lewis碱位 Mo=O 与金属Cu位上形成Cu-C(CH2)(CH3)-H→O=Mo吸附态. Cu/MoO3-TiO2催化剂吸收阈值蓝移和光吸收量的提高均有利于其催化活性的提高,Cu/10%MoO3-TiO2 光催化剂的催化活性优于其它MoO3含量的催化剂,光量子产率达22.8%,在110 ℃,0.1 MPa,空速200 h-1和125 W紫外灯辐照下,C3H6转化率为8.4%,MAA选择性超过95%. 提出了催化剂光促表面催化CO2与C3H6合成MAA的反应机理.     

单茂钪催化剂（C5H5）Sc（CH2C6H4NMe2-o）2合成高顺式窄分布聚丁二烯

合成了6种单茂稀土催化剂Cp’LnR2(THF)n(其中,Cp’=C5H5,C5Me4SiMe3;R=CH2C6H4NMe2-o,CH2SiMe3;Ln=Sc,Y,Lu;n=0或1),并以[Ph3C][B(C6F5)4]为助催化剂,甲苯为溶剂,考察催化剂结构对丁二烯聚合活性,立体选择性,催化剂利用率以及聚合物分子量和分子量分布的影响.通过1H-NMR,13C-NMR,FTIR,GPC以及DSC对聚丁二烯进行表征,结果表明,当Cp’=C5H5,R=CH2C6H4NMe2-o,Ln=Sc,n=0时,催化剂(C5H5)Sc(CH2C6H4NMe2-o)2对丁二烯聚合活性最高,可达9600 kg-polymer/mol-Sc·h,催化剂利用率为45%,聚丁二烯顺-1,4结构含量在96%~98%之间,分子量分布窄,指数在1.3左右;以甲苯或氯苯作为聚合溶剂时,聚合活性最高,聚丁二烯分子量保持窄分布,在所有溶剂中聚丁二烯顺-1,4结构含量均达到96%以上;催化剂聚合活性随温度下降而降低,而聚合物分子量分布有变窄的趋势,温度对聚丁二烯立体选择性无明显影响;当[Bd]/[Sc]摩尔比从500增加到3000时,聚合反应1 min转化率均达到100%,聚丁二烯分子量呈可控线性增大,最高达44.6×104,且均保持聚合物窄分布.DSC谱图表明聚丁二烯Tg为-107℃,当升降温速率为10 K/min时,在-63℃和-8℃附近呈现出明显的冷结晶峰和熔融峰.     

[Co(en)3]2(Zr2F12)(ZrF6H2O)·H2O的合成、 结构及表面光电压性质

采用常温晶化法合成了1个新的金属配合物与氟化锆的复合物[Co(en)3]2(Zr2F12)(ZrF6H2O)·H2O(1), 并对其单晶结构进行了解析. 该化合物属单斜晶系, C2/c 空间群, a=3.06110(17) nm, b=0.877680(5) nm, c=1.50811(9) nm, β=118.897(4)°, V =3.547(4) nm3, Z=8. 该化合物由双核氟化锆阴离子簇 [Zr2F12]4-和单核氟化锆阴离子簇 [ZrF6H2O]2-与钴胺配合物阳离子 [Co(en)3]3+ 及水分子组成, 氟化锆与钴胺配合物之间存在大量的氢键. 该化合物的表面光电压谱在339 nm处出现了光电信号. 这种特殊的光电现象有可能归因于该化合物的钴胺配合物阳离子与氟化锆阴离子簇之间存在的协同作用.     

含SR桥的双核钼(I)配合物Mo2(CO)8-n(SR)2Ln的新合成途径和Mo2(C(O)6(SPh)2(MeCN)2的结构研究

经由零价双核钼含SR桥的配合物的氧化反应合成了一系列含各种SR桥的双核钼(I)配合物Mo2-(CO)8-n(μ-SR)2Ln(R=Br^t, Ph, Bz(C6H5CH2), CH2CO2Et;L=MeCN, PPh3; n=0,2]. 并应用红外光谱、元素分析等进行表征, 讨论了新的合成途径. 含MeCN配位体配位到Mo(I)上的配合物, Mo2(CO)6(SPh)2(MeCN)2经X射线结构测定, 系属单斜晶系, 空间群P21/c,a=9.241(2), b=9.330(3), C=15.458(4)A:β=105.77(2)°V=1283(1)A^3; Z=2; R=0.033. Mo-Mo距离为2.978A, 表明其Mo-Mo距离为2.978A, 表明其Mo-Mo键的形成, Mo-S键长为2.469A. 比较同系物Mo2(CO)8(μ-SCH2CO2-Et)2, Mo2(CO)6(μ-SCH2CO2Et)2(MeCN)2和Mo2(CO)8(μ-SBu^t)2的结构, 并讨论其结构与化学.     

Synthesis, Characterization and Crystal Structure of [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2]

The reaction of μ-alkyne-bridged dimolybdenum compound [Mo2(μ-C2HPh)(CO)4(η5-C5H4C(O)Me)2] 1 with Co2(CO)8 in refluxing toluene gave a new butterfly compound [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2] 2 which was fully characterized by elemental analysis, IR, 1H NMR and X-ray single crystal diffraction techniques. 2 crystallized in monoclinic system, C30H20Co2Mo2O10, Mr=850.23, space group P21/a(#14), a=14.165(5), b=12.498(2), c=16.204(2)(A), β = 96.50(2)°, V = 2850(1)(A)3, Z = 4, Dc = 1.981 g cm-3, F(000)=1672, μ(MoKα)=20.41 cm-1, final R=0.030, Rw=0.039 for 4831 observable reflections with I>2σ(I). The structure contains a Co2Mo2 butterfly core, and each Mo-Co bond is spanned by an asymmetric semi-bridging carbonyl ligand.     

含SR桥的双核钼(I)配合物Mo2(CO)8-n(SR)2Ln的新合成途径和Mo2(C(O)6(SPh)2(MeCN)2的结构研究

经由零价双核钼含SR桥的配合物的氧化反应合成了一系列含各种SR桥的双核钼(I)配合物Mo2-(CO)8-n(μ-SR)2Ln(R=Br^t, Ph, Bz(C6H5CH2), CH2CO2Et;L=MeCN, PPh3; n=0,2]. 并应用红外光谱、元素分析等进行表征, 讨论了新的合成途径. 含MeCN配位体配位到Mo(I)上的配合物, Mo2(CO)6(SPh)2(MeCN)2经X射线结构测定, 系属单斜晶系, 空间群P21/c,a=9.241(2), b=9.330(3), C=15.458(4)A:β=105.77(2)°V=1283(1)A^3; Z=2; R=0.033. Mo-Mo距离为2.978A, 表明其Mo-Mo距离为2.978A, 表明其Mo-Mo键的形成, Mo-S键长为2.469A. 比较同系物Mo2(CO)8(μ-SCH2CO2-Et)2, Mo2(CO)6(μ-SCH2CO2Et)2(MeCN)2和Mo2(CO)8(μ-SBu^t)2的结构, 并讨论其结构与化学.     

七配位二聚体配合物{(PhCH2)2Sn·[2,6-(O2C)2C5H3N](CH3OH)}2的合成及结构

在三乙胺存在下利用三苄基氯化锡和2,6-吡啶二甲酸,以1:1摩尔比反应,合成了七配位二聚体{(PhCH2)2Sn[2,6-(O2C)2C5H3N](CH3OH)}2.通过元素分析、红外光谱和核磁共振氢谱对其结构进行了表征.用X射线单晶衍射法测定了该化合物的晶体结构.化合物为三斜晶系,P1空间群,晶胞参数a=0.9625(6)nm,b=1.0947(9)nm,c=1.996(3)nm,α=90.00(2)°,β=87.69(3)°,γ=90.00(3)°,Z=2,V=2.102(6)nm3,μ=1.248mm-1,F(000)=1000,R1=0.0476,wR2=0.0782.化合物中2个锡原子呈七配位畸变五角双锥构型.生物活性测试结果表明,该化合物具有较强的体外抗肿瘤活性.     

配合物(ArO)2Yb(NPh2)2K(THF)4(Ar=C6H2-t-Bu3-2,4,6)的合成、分子结构和催化行为

Reaction of anhydrous YbC13 with 2 equiv, of sodium 2,4,6-tri-tert-butylphenoxide (ArONa, Ar=C6H2-t-Bu3-2,4,6) and 2 equiv, of potassium diphenyl amide in THF afforded the first bis(aryloxo) amido-lanthanide complex of (ArO)2Yb(NPh2)2K(THF)4 (1). In 1, the ytterbium and potassium were bridged via diphenyl amido ligands.The ytterbium metal center was coordinated to two oxygen atoms of aryloxide ligands and two nitrogen atoms of diphenyl amido ligands in a conventional distorted tetrahedral fashion, while the potassium interacted in η^2-fashion with two phenyl rings of the diphenyl amido ligands besides four THF molecules. 1 displayed moderate catalytic activities for the polymerization of methyl methacrylate and acrylonitrile.     

异核四面体簇合物(η5-C5H5)(η5-RC5H4)MNiFeS(Co)5(M=MO,W)的合成及等瓣置换反应研究——(η5-C5H5)(η5-MeO2CC5H4)MONiFe2S(CO)10的单晶分子结构

通过(η5-RC5H4)MCoFeS(CO)8(la:M=Mo,R=H;1b:M=Mo,R=MeO2C;lc:M=Mo,R=Me;1d:M=Mo,R=EtO2C;1e:M=W R=H)与Cp2Ni的等瓣置换反应合成了簇合物(η5-C5H5)(η5-RC5H4)MNiFeS(CO)5(2a:M=Mo,R=H;2b:M=Mo,R=MeO2C;2c:M=Mo,R=Me;2d:M=Mo,R=EtO2C;2e:M=W,R=H).进一步通过2a,b与Co2(CO)8以及2c,d与Fe2(CO)9的等瓣置换反应,分别合成了(η5-RC5H4)MoCoFeS(CO)8(la:R=H;1b:R=MeO2C)和(η5-C5H5)(η5-RC5H4)MoNiFe2S(CO)10(3a:R=Me;3b:R=EtO2C).新簇合物2c-e和3a,b的结构均经元素分析、IR及1H NMR谱学表征.此外,还对我们以前合成的一个3a,b类似物(η5-C5H5)(η5-MeO2CC5H4)MoNiFe2S(CO)10(3c)成功地进行了单晶结构分析.3c属单斜晶系,Cc(#9)空间群,晶胞参数a=1.0051(3)nm,b=1.5311(5)nm,c=1.7437 nm,β=105.5(3)°,Z=4.最终一致性因子R=0.025,Rw=0,033.     

簇合物C03(CO)7(μ3-S) [μ,η2-CNP(S)(C6H4OCH3)OC(Ph)CH]和Co3(CO)7(μ3-S) [μ,η2-SCNC(CH3)2P(S)(Cl)N(Ph)]的合成与晶体结构

用Co2(CO)8分别与两个杂环配体C(S)NHP(S) (C6H4OCH3)OC(Ph)CH (L1)和C(S)NHC(CH3)2P(S) (CI)N(Ph) (L2)反应.合成两个新的三核钴羰基硫簇合物Co3(CO)7(μ3-S) [μ,η2-CNP(S) (C6H4OCH3)OC(Ph)CH] (Ⅰ)和Co3(CO)7(μ3-S) [μ,η2-SCNC(CH3)2P(S) (CI) N(Ph)] (Ⅱ).用元素分析,IR,1H NMR,31P NMR 及 MS谱表征了它们的结构,同时用X射线衍射法测定了它们的晶体分子结构,二者属于三斜晶系,P1空间群,I的晶胞参数为:a=0.84768(1)nm,b=1.19049(3)nm,c=1.43639(1)nm,α=86.926(1)°,β=81.60l(3)°,γ=88.535(2)°,V=1.4318(5)nm3,Z=2,Dc=1.641g@em-3,F(000)=716,μ=1.893mm-1,R=0.0602,Rw=0.1515.Ⅱ的晶胞参数为:a=1.2050(2)nm,b=1.2448(2)nm,c=0.8951(2)nm,α=97.49(1)°,β=93.552(4)°,γ=108.432(3)°,V=1.2554(3)nm3,Z=2,Dc=1.84lg@cm-3,F(000)=690,μ=2.419mm-1,R=0.0423,Rw=0.1075.Ⅰ和Ⅱ的分子骨架Co3S为三角锥构型,S作为面桥基配体,所有C0作为端基配体与三个Co原子成键.I中含有CoCoCN四元环组件,Ⅱ中含有CoCoSCN五元环组件.     

一个新的Tutton盐Na2[Co(H2O)6](SO4)2的结构与性能研究

采用溶液法合成了一个新的Tutton盐Na2[Co(H2O)6](SO4)2通过红外光谱和X-射线单晶衍射对其进行了表征.晶体结构分析表明该化合物晶体属单斜晶系,P21/c空间群,晶胞参数:a=0.6185(2)nm,b=1.2334(3)um,c=0.9137(1)nm,β=105.775(1)°,V=0.67078(2)nm3,Z=2.固体粉末紫外可见透射光谱是不连续的,具有较高的透过率和较窄的带宽(300～450 nm).用循环伏安法研究了化合物的电化学性质,发现Na2[Co(H2O)6](SO4)2掺杂氢氧化镍电极片的氧化还原峰电流均有较大提高,电极反应活性明显增加.     

新型超分子化合物(H3NCH2CH2NH3)2[(HPO4)2Mo5O15]的晶体结构

首次通过水热方法合成了新型超分子化合物(H3NCH2CH2NH3)2[(HPO4)2Mo5O15]的晶体结构,并通过X衍射进行了结构表征,晶体学数据为:单斜晶系,C2/c空间群,a=1.766 6(4)nm,b=1.003 4(2)nm,c=1.376 7(3)nm,α=90°,β=96.90(3)°,γ=90°,ν=2.422 7(8)nm3,Z=4,R=0.043 1,wR2=0.128 7.