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1.
用5-甲基水杨醛、4-二乙氨基水杨醛分别与卡巴肼或硫代卡巴肼缩合,制得1,5-二取代卡巴肼或硫代卡巴肼配体。在微波甲醇溶剂热条件下,二苄基二氯化锡前体与配体反应,合成了双(取代水杨醛)缩(硫代)卡巴肼苄基锡配合物T1~T4,但T4的结构与T1~T3不同,T4由N,N′-双(4-二乙氨基水杨醛)缩连氮及甲氧基桥联锡组成的苄基锡配合物,T4还可由卡巴肼、4-二乙氨基水杨醛和二苄基二氯化锡"一锅法"合成。T1~T4的结构经元素分析、IR、1H/13C NMR表征,并用X射线衍射法确证配合物T4的晶体分子结构。T4属单斜晶系,P21/c空间群,中心锡原子与氮、氧、苄基碳和氯原子组成六配位变形八面体构型。T4在DMF-H2O溶液中具有良好的荧光性质,当含水量0~30%(V/V)时具有聚集荧光增强效应,含水量大于30%时,随含水体积分数增加荧光强度减弱,以至最后淬灭。配合物对马齿苋具有良好的生长抑制作用,T1和T3对决明子、T2对苋菜和T4对四九菜心具有选择性生长抑制作用,可作为除草剂的候选化合物进一步研究。  相似文献   

2.
卡巴肼分别与水杨醛和香草醛缩合制备1,5-不对称二取代卡巴肼配体,在甲醇溶剂热中,正丁基三氯化锡与配体反应,合成1-(水杨醛)-5-(香草醛)缩卡巴肼丁基锡配合物(B1)和含N,N′-双水杨醛缩连氮分子的丁基锡配合物(B2),经元素分析,IR,1H、119Sn、13C NMR和X射线衍射晶体结构表征,配合物(B1)、(B2)晶体分别属单斜晶系、P21/n空间群和三斜晶系、P1空间群,中心锡与配基原子构成六配位畸形八面体构型,配合物(B1)在DMF-H2O溶剂体系中具有良好的荧光性质,当含水0~10%(V/V)时具有聚集荧光增强效应,含水量大于10%,随含水体积分数增加荧光强度减弱,以至最后淬灭。配体及其配合物(B1)对马齿苋、刺苋、决明子、四九菜心和苋菜5种靶标植物均具有一定生长抑制作用,尤其是配体对马齿苋、刺苋的生长有良好的抑制作用,配合物可以选择性抑制决明子的生长,可作为决明子除草剂的候选化合物。  相似文献   

3.
微波甲醇溶剂热中,二丁基氧化锡与双(3,5-二叔丁基水杨醛)缩卡巴肼(H_2L~1)及缩硫代卡巴肼(H_2L~2)反应,合成了2个二丁基锡双核配合物[(Bu_2Sn)_2L]·MeOH,对其进行了元素分析、IR、~1H和~(13)C NMR结构表征。X射线晶体衍射结构表明:配合物1和2具有类似结构的双锡核配合物,Sn1和Sn2分别与配基原子构成畸形三角双锥和畸形八面体构型。相邻分子间通过O-H…N氢键作用,形成一维无限链状结构。配合物1和2对马齿苋、刺苋以及决明子等杂草的根和茎的生长具有明显的抑制作用。  相似文献   

4.
黑嘉慧  杨莉宁  李珺 《应用化学》2019,36(8):949-957
基于TiO2光催化性能的染料敏化改性,采用2-噻吩甲醛缩合乙二胺合成了席夫碱配体L,并与金属配合得到了金属配合物[ZnLCl2](1),[NiL'(NO3)2](2)(L'为单噻吩醛缩乙二胺),对配体L、配合物1 和2进行了X射线单晶衍射结构分析。 用合成的配体和配合物修饰TiO2得到相应的复合光催化剂L-TiO2、1-TiO2和2-TiO2,并进行了红外光谱、紫外-可见漫反射光谱、粉末X射线衍射图谱等表征,研究了这3种光催化剂降解水中有机污染物4-硝基酚(4-NP)和罗丹明B(RhB)的催化活性。 结果表明,1-TiO2、2-TiO2可以有效的降解4-NP和RhB,降解率可达90%以上。  相似文献   

5.
合成了2,5-二甲氧基-N,N'-双(4-吡啶基)对苯二甲酰胺(简称为dmbpt), 并以其和1,3,5-苯三甲酸(简称为H3btc)为配体合成了2个新配合物[Cd2(dmbpt)2(Hbtc)2]·2DMF·C2H7N·H2O(1)和[Cd3(dmbpt)2(btc)2]·4H2O(2). 配合物1是具有3,5L2拓扑的二维金属有机骨架; 配合物2是具有jcr7拓扑的三维金属有机骨架, 这是一个稀有的拓扑结构. 配合物1和2都含有二级结构单元Cd2(—COO)4(—Py)4. 在结构关系上, 配合物2的三维网络可以看作是由配合物1的二维网络通过形成新的配位键连接而成的. 在原料和溶剂相同的溶剂热反应条件下, 能以不同比例同时获得2种配合物. 产物中配合物1和配合物2的比例可以通过改变反应物的浓度来调控, 这可能与由DMF分解产生的二甲胺促进H3btc的去质子化有关.  相似文献   

6.
在甲醇溶液中,卡巴肼、(4-二乙氨基)水杨醛和二乙酸二丁基锡"一锅法"反应,合成了一个新颖的基于双(4-二乙氨基水杨醛)缩偶氮二甲酰肼(L)的七配位有机锡配合物[Sn(L)(n-butyl)_2]n(T)。经元素分析、IR、(1H,119Sn,13C)NMR和X射线衍射晶体结构表征,T的晶体属单斜晶系C2/c空间群,中心锡周围由双(4-二乙氨基水杨醛)缩偶氮二甲酰肼的O,N配位原子占据赤道位置和2个丁基占据顶端位置形成畸变五角双锥构型。通过烯醇式氧原子的桥联配位作用,T向一维带状无限扩展产生"竹筏状"超分子结构。配合物T在二甲基甲酰胺、四氢呋喃、乙醇、甲醇和甲苯有机溶剂及其有机溶剂-水混合物中具有强荧光发射峰,当含水量的体积分数在0~10%(V/V)时具有良好的聚集荧光增强效应,含水量大于10%(V/V)时发生荧光淬灭。  相似文献   

7.
采用水热方法合成了4种Sm3+配合物, 即{[SmZn(2,5-pdc)2(tp)0.5(H2O)]·2H2O}n(1), [Sm2Zn2(C6H5COO)10(Imh)2(H2O)2](2), {[Sm2(NO2C6H4COO)6(H2O)4]·H2O}n(3)和{[SmN(CH2COO)3(H2O)2]·H2O}n(4)[2,5-pdc=2,5-吡啶二羧酸根, tp=对苯二甲酸根, C6H5COO=苯甲酸根, Imh=咪唑, NO2C6H4COO=对硝基苯甲酸根, N(CH2COO)3=氨三乙酸根]. 通过单晶X射线衍射确定了其晶体结构. 在室温下测定了其红外光谱、 紫外-可见-近红外光谱以及在近红外区和可见区的发射光谱. 结果表明, 4种配合物在近红外区或可见区均出现Sm3+离子的特征发射. 这是形成配合物后, Zn-配体部分和配体对Sm3+离子发光的敏化作用所致. 此外, 讨论了不同有机配体或d过渡金属离子对Sm3+离子发光的影响, 并分析了配合物中Sm3+离子的近红外发射带位移、 劈裂和加宽的原因.  相似文献   

8.
用常规溶液法由氯化锰(MnCl2·4H2O)和4-甲基-1,2,3-噻二唑-5-甲酸(HL)反应制备了配位聚合物[Mn3(L)6(H2O)4]n(1),加入配体菲咯啉(phen)后合成了配合物[Mn2(phen)4(H2O)2Cl2](L)2·3H2O (2)。用元素分析、红外光谱、热重分析及单晶X射线衍射进行了配合物的表征。单晶结构分析表明:配合物1属单斜晶系P21/c空间群,3个锰离子通过6个L-中的氧原子双齿桥联,形成了线型三核簇合物单元,簇合物单元间又通过其中一个噻二唑环上的氮原子与另一个簇合物单元的锰原子配位,形成层状结构;配合物2属三斜晶系■空间群,锰离子分别与1个氯离子、1个水分子和2个phen分子中的4个氮原子配位,形成六配...  相似文献   

9.
使用多齿希夫碱配体通过溶剂热的方法合成了一例新的Ho4配合物,即[Ho4(NO3)2(acac)4(L)2(CH3OH)2]·2CH3CN,其中H4L=(E)-2-(羟甲基)-2-(((2-羟基萘-1-基)亚甲基)氨基)丙烷-1,3-二醇,acac=乙酰丙酮。X射线衍射分析表明,配合物呈中心对称的四核结构,中心的Ho1(Ⅲ)和Ho2(Ⅲ)均为八配位的三角十二面体几何构型。配合物1具有良好的溶剂稳定性。磁性研究表明配合物1具有慢磁弛豫行为。据我们所知,配合物1是一例少有的在零直流场下具有慢磁驰豫行为的Ho4配合物。值得一提的是,配合物1在催化CO2与环氧化合物的环加成反应中表现出较高的催化活性。  相似文献   

10.
通过由Fe3(CO)12、RSH和Et3N所形成的[(μ-CO)(μ-RS)Fe2(CO)6]Et3NH于室温下分别与对或间苯二甲酰氯的原位反应,首次合成6个结构新颖的苯二甲酰基桥联铁硫配合物[(μ-RS)·Fe2(CO)6]2(μ-p-OCC6H4CO-p-μ)(R=Et,n-Bu,t-Bu)以及[(μ-RS)Fe2(CO)6]2(μ-m-OCC6H4CO-m-μ)(R=n-Pr,n-Bu,t-Bu).经元素分析、IR光谱及1HNMR表征了它们的结构,并讨论了产物的生成过程.此外,还提出了合成对苯二甲酰氯的一种新方法.  相似文献   

11.
新型桥联双四面体簇合物的合成与表征   总被引:2,自引:0,他引:2  
利用(μ3-CCO2Et)Co3(CO)9与单阴离子试剂[Mo(CO)35-C5H4R)]-[R=H,C(O)Me]的反应合成了2个新的含CCo2Mo骨架的簇合物(μ3-CCO2Et)Co2Mo(CO)85-C5H4R)[R=H(1);R=C(O)Me(2)],进而用其与双阴离子试剂{-M(CO)35-C5H4C(O)]}2-1,4-C6H4[M=Mo,W]反应合成了4个双四面体簇合物{(μ3-CCO2Et)CoMoM(CO)75-C5H4R)[η5-C5H4C(O)]}2-1,4-C6H4[M=Mo,R=H(3);M=Mo,R=C(O)Me(4);M=W,R=H(5);M=W,R=C(O)Me(6)].这6个化合物的C和H元素分析,IR,1HNMR等表征都与其结构一致.晶体X射线衍射分析表明,化合物2属单斜晶系,C2/c空间群,晶胞参数a=1.1264(3)nm,b=1.1879(3)nm,c=3.3565(10)nm,β=93.320(5)°,V=4.484(2)nm3,Z=8,Dc=1.867g·cm-3,F(000)=2480,R=0.0369,wR=0.1150.  相似文献   

12.
四甲基二硅桥连取代环戊二烯基配体相继与丁基锂及MCl4·2THF作用,生成四甲基二硅桥连取代环戊二烯基钛和锆化合物(Me2SiSiMe2)(C5H4R)(C5H4R')MCl2[R=H,R'=t-Bu,M=Ti(1),Zr(2),Hf(3);R=H,R'=Me,M=Ti(4);R=R'=Me,M=Ti(5),Zr(6)].通过元素分析、MS和1HNMR谱表征了化合物的分子结构,并通过X射线衍射分析测定了化合物1的晶体结构.研究了在甲基铝氧烷(MAO)的助催化下,化合物1-3和6对乙烯聚合的催化性能。  相似文献   

13.
The reaction of trans-X(CO)4WCNR2 (X = Br, R = c hex (cyclohexyl); X = Cl, R = c hex, ipr (isopropyl) with M+X (M+ = NEt4+, X = Br; M+ = PPN+, X = Cl) leads under substitution of one CO ligand to new anionic dihalo(tricarbonyl)carbyne-tungsten complexes of the type M+ mer-[(X)2(CO)3WCNR2] (M+ = NEt4+, X = Br, R = c hex; M+ = PPN+, X = Cl, R = c hex, i pr), whose composition and structure were determined by elemental analysis as well as by IR, 1H and 13C NMR spectroscopy. In the anionic carbyne complexes the entered halogen ligand, coordinated in a cis position relative to the carbyne ligand on the metal, can be easily substituted by neutral nucleophiles, as the reaction of PPN+ mer-[(Cl)2(CO)3WCNchex2] with PPh3 demonstrates yielding the neutral carbyne complex mer-[Cl(CO)3(PPh3)WCNchex2].  相似文献   

14.
The following structural peculiarities of the agostic acyl structure 2R) (R = H, SiMe3) and some characteristic chemical reactivity of the M-η2-acyl and iminoacyl linkage are described. (i) A structural comparison of the bonding parameters within three agostic acetyl Mo complexes containing the dithioacid ligand, indicates that the agostic interaction strengthens upon increasing the electron-releasing properties of the S-chelating ligand. (ii) The acyl-xanthate complex Mo(C(O)Me)(S2COR)(CO)(PMe3)2 undergoes loss of a sulfur atom from the coordinated xanthate and coupling with the acyl ligand to form complexes containing coordinated alkoxythiocarbonyl and monothioacetate ligands. The latter can be metathetically replaced by KS2COR. (iii) Upon heating at 70°C η2-acyl-dicarbonyl bispirazolilborate complexes of molybdenum of the type Mo(H2B(pz*)2)(η2-C(O)Me)(CO)2(PMe3) (pz* = 3,5-dimethyl-pyrazol-1-yl) yield functionalized acyl ligands derived from the stereo- and regioselective intramolecular addition of one of the B---H bonds of the H2B(pz*)2 group across the C=O moiety of the η2-acyl group. (iv) The η2-acyl-isocyanide complexes {Mo}(η2-C(O)R)(CNR′) ({Mo} = Mo(H2B(pz*)2)(CO)(PMe3)) undergo irreversible thermal isomerization to the corresponding η2-iminoacyl-carbonyl derivatives {MO}(η2-C(NR′)R)(CO). This isomerization reaction follows first-order kinetics.  相似文献   

15.
A detailed in situ 13C and 1H NMR spectroscopic characterization of the following families of alkylperoxo complexes of titanium is presented: Ti(η2-OOtBu)n(OiPr)4−n, where n = 1–4; binuclear complexes [(iPrO)3Ti(μ-OiPr)2Ti(OiPr)22-OOtBu)] and [(η2-OOtBu)(iPrO)2Ti(μ-OiPr)2Ti(OiPr)22-OOtBu)]; complexes with β-diketonato ligands: Ti(LL)2(OEt)(η2-OOtBu), Ti(LL)2(OiPr)(η2-OOtBu), Ti(LL)22-OOtBu)2, Ti(LL)2(OtBu)(η1-OOtBu), where HLL = acetylacetone, dipivaloylmethane. These alkylperoxo complexes could not be isolated due to their instability and were studied in situ at low temperatures. Whereas the side-on (η2) coordination mode of tert-butylperoxo ligand is generally preferable, the end-on (η1) coordination caused by spatial hindrance from surrounding bulky ligands is found in two cases. The quantitative data on the reactivity of alkylperoxo complexes found towards sulfides and alkenes were obtained. The system TiO(acac)2/tBuOOH in C6H6 was reinvestigated using 13C and 1H NMR spectroscopy. The structure of the complex Ti(acac)2{CH3C(O)(OOtBu)COO} actually formed in this system was elucidated. Four types of titanium(IV) alkylperoxo complexes were detected in the Sharpless–Katsuki catalytic system using 13C NMR spectroscopy.  相似文献   

16.
The reaction of bis(pyrazol-1-yl)methane tetracarbonylmolybdenum(0) or tungsten(0) complexes with RSnCl3 (R=Ph, Cl) at room temperature yielded heterobimetallic complexes CH2(Pz)2M(CO)3(Cl)(SnCl2R) (Pz represents substituted pyrazole; M=Mo or W; R=Ph or Cl) in good yields, which have been characterized by elemental analysis, 1H NMR and IR spectroscopy. The reaction of bis(3,5-dimethyl-4-halopyrazol-1-yl)methane tetracarbonyl tungsten with PhSnCl3 did not take place even in refluxing CH2Cl2. The electronic and steric characteristics of substituents on the pyrazole ring remarkably influence the structures of the products. The structures of CH2(3,5-Me2-4-BrPz)2W(CO)3(Cl)(SnCl3) (8) and CH2(4-BrPz)2Mo(CO)3(μ-Cl)(SnCl2Ph) (17) (Pz: pyrazole) determined by X-ray crystallography show that no chlorine-bridged W---Sn bond is observed in complex 8, while one chlorine-bridged Mo---Sn bond exists in complex 17. The Sn---M bond length is 2.7438(5) Å in complex 8 (W---Sn) and 2.7559(4) Å in complex 17 (Mo---Sn).  相似文献   

17.
The reaction of [Nb(η5-C5H4R)2X2] [1: R = SiMe3, X = Cl; 2: R = SiMe3, X = Br; 3: R = H, X = Cl; 4: R =t, X = Cl] with nitroso derivatives ArNO [a: Ar = Ph; b: Ar = o-CH3-C3H4; c: Ar = p-(CH3)2NC6H4] yields paramagnetic complexes formulated as [Nb(η5-C5H4R)(η3-C5H4R)X2(ArNO-N,O) 1a, 1b, 1c, 2a, 3a, 4a and 4c, which have been characterized by ESR and IR spectroscopy.  相似文献   

18.
Two ligands [ortho-C6H4NR2(CH2NH)]2CH2CH2(3: R=Me; 4: R=EO were prepared by the reduction of preligands [ortho-C6H4NR2(CH=N)]zCH2CH2(1: R=Me; 2: R=Et). These ligands reacted with AIMe3 to afford the corresponding dinuclear aluminum complexes {A1Me2[ortho-C6H4NR2(CH2N)]}2CHzCH2(5: R=Me; 6: R=Et). All the compounds were characterized by 1H and UC nuclear magnetic resonance(NMR) spectroscopies and elemental analyses. The catalytic properties of the aluminum complexes towards the ring-opening polymerization of lactones were investi- gated in the presence of benzvl alcohol. All the oolvmerization reactions were proceeded in a controlled manner.  相似文献   

19.
The chemistry of the di-μ-methylene-bis(pentamethylcyclopentadienyl-rhodium) complexes is reviewed. The complex [{(η5-C5Me5)RhCl2}2] (1a) reacted with MeLi to give, after oxidative work-up, blood-red cis-[{(η5-C5Me5)Rh(μ-CH2)}2(Me)2], 2. This has the two rhodiums in the +4 oxidation state (d5), and linked by a metal-metal bond (2.620 Å). Trans-2 was formed on isomerisation of cis-2 in the presence of Lewis acids, or by direct reaction of 1a with Al2Me6, followed by dehydrogenation with acetone. The Rh-methyls in [{(η5-C5Me5)Rh(μ-CH2)}2(Me)2] were readily replaced under acidic conditions (HX) to give [{(η5-C5Me5)Rh(μ-CH2)}2(X)2] (X = Cl, Br or I); these latter complexes reacted with a variety of RMgX to give [{(η5-C5Me5)Rh(μ-CH2)}2(R)2] (R = alkyl, Ph, vinyl, etc.). Trans-2 also reacted with HBF4 in the presence of L to give first [{(η5-C5Me5)Rh(μ-CH2)}2(Me)(L)]+ and then [{(η5-C5Me5)Rh(μ-CH2)}2(L)2]2+ (L = MeCN, CO, etc.). The {(η5-C5Me5)Rh(μ-CH2)}2 core is rather kinetically inert and also forms a variety of complexes with oxy-ligands, both cis-, e.g. [{(η5-C5Me5)Rh(μ-CH2)}2(μ-OAc)]+ and trans-, such as [(η5-C5Me5)Rh(μ-CH2)}2(H2O)2]2+. The complexes [{(η5-C5Me5)Rh(μ-CH2)}2(R)L]+ (R = Me or aryl) in the presence of CO, or [{(η5-C4Me5)Rh(μ-CH2)}2(R)2] (R = Me, Ph or CO2Me) in the presence of mild oxidants, readily yield the C---C---C coupled products RCH=CH2. The mechanisms of these couplings have been elucidated by detailed labelling studies: they are more complex than expected, but allow direct analogies to be drawn to C---C couplints that occur during Fischer-Tropsch reactions on rhodium surfaces.  相似文献   

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