共查询到19条相似文献,搜索用时 140 毫秒
1.
硼化合物研究——ⅩⅪ.H[B12H11NH2COR]与Ln2O3的反应——一类新型的含硼希土(Ⅲ)化合物的合成 总被引:1,自引:0,他引:1
将硼烷衍生物(C_2H_5)_4NB_(12)H_(11)NH_2COR[R=-CH-3,—CH=CH_2]经离子交换而得到的酸H[B_(12)H_(11)NH_2COR]与希土氧化物作用,制得一系列分子式为L-n[B_(12)H_(11)NH_2COR]_3·5H_2O的化合物,再用氧化吡啶(pyO)与上述化合物反应,就得到了分子式为[Ln(pyO)_6](B_(12)H_(11)NH_2COR)_3的新型化合物。 相似文献
2.
将闭式+氢+硼酸阴离子酰胺衍生物[B10H9NH2COCH=CH2]-、双苯甲酰丙酮缩1,3-丙二胺C6H5C(OH)=CHC(CH3)=N(CH3)CH=C(OH)C6H5(Bapn)及希土氯化物在丙酮-乙醇混合溶剂中进行反应,得到分子式为Ln(Bapn)3[B10H9NH2COCH=CH2]3(Ln=La,Nd,Sm,Eu,Gd,Dy)的混式配体希土配合物。通过元素分析、IR、1H NMR及摩尔电导率的测定对配合物进行了表征,还通过DTA-TG方法研究了它们的热性质。 相似文献
3.
希土二氯醋酸盐与邻菲罗啉(phen)混配配合物合成和表征 总被引:3,自引:0,他引:3
本文采用一种新的合成方法在水、乙醇和四氢呋喃混合溶剂中合成了6种希土二氯醋酸盐与邻菲罗啉(phen)混配配合物,通过元素分析、红外光谱、差热-热重和紫外光谱等分析测试手段研究了配合物的性质,并确定配合物的组成为:Ln(CCl_2HCOO)_3(phen)_2·2H_2O[Ln=Gd、Tb、Er、Yb]和Ln(CCl_2HCOO)_3(phen)_2·H_2O·C_2H_5OH[Ln=Pr、Nd]. 相似文献
4.
制备了Pr、Yb两种希土元素异硫氰酸(?)与苄胺的固体配合物.并对其进行了组成分析、红外光谱分析、X射线衍射物相分析和热重分析.测量了298.15K时两种固体配合物RE(NCS)_3·4C_6H_5CH_2NH_2在HCl水溶液中的反应热和相应的两种希土元素异硫氰酸盐水合物RE(NCS)_3·n_1H_2O(RE为Pr时,n_1=7;RE为Yb时,n_1=6)在C_6H_5CH_2NH_2-HCl-H_2O溶液中的积分溶解热以及苄胺C_6H_5CH_2NH_2在HCl水溶液中的反应热.藉助本文所设计的热化学循环,求得了这两种配合物的标准生成焓,还计算了它们的晶格能. 相似文献
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本文在乙醇-水溶液中合成了H_2DBA及phen、[OH]~-与希土离子的混配配合物Ln(HDBA)_2(OH)(phen)·H_2O(Ln=La、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Y)十三个.通过化学分析,元素分析及电导分析确定了配合物的组成;研究了配合物的紫外、红外光谱及热行为,并对可能的配合物结构进行了推测. 相似文献
7.
环戊二烯基希土氯化物是一类合成希土有机配合物的重要前身。尽管在1980年前没能成功地合成含轻希土元素的这类配合物,但目前已发现,采用具有较大体积的取代环戊二烯做配体,如C_5Me_5H,C_5H_3〔Si(CH_3)_3〕_2H,C_5Me_4C_3H_7H和桥联的配体(C_5H_4)_2(CH_2)_3H_2都可得到相应的取代环戊二烯基轻希土氯化物。控制LnCl_3和CpNa的反应摩尔比也可以成功地得到这类轻希土的环戊二烯基氯化物。 相似文献
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双齿配体八配位镧系配合物的结构化学研究——Ⅱ.[C4H9O]+[Ln(S2CNC4H8)4]-(Ln=La和Nd)的合成和结构 总被引:4,自引:0,他引:4
镧系配合物[C_4H_9O]~+[Ln(S_2CNC_4H_8)_4]~-是从LnCl_3(Ln=La和Nd)和NH_4(S_2CNC_4H_8)在THF中反应得到的。 [C_4H_9O]~+[Ln(S_2CNC_4H_8)_4)~-的晶体和分子结构通过单晶X-射线结构分析获得,结晶学参数列于下表。 晶体结构是从Patterson和Fourier方法解出,并用全矩阵最小二乘法修正。最后偏离因子对于La配合物,R=0.064,R_w=0.0681;而对于Nd配合物;R=0.051,R_w=0.059。晶体由正离子[C_4H_9O]~+和负离子[Ln(S_2CNC_4H_8)4]~-组成,在负离子中ln原于是由八个硫原子构成扭变的三角形十二面体配位。Ln-S平均距离分别为2.974(La)和2.908(Nd)。 相似文献
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制备了由2,6-二乙酰吡啶与肼基硫代甲酯衍生的希夫碱C_5H_3N[CH=NN=C(S)XR]_2(X=S,R=CH_3,C_6H_5CH_2;X=O,R=C_6H_5CH_2)。离析出类型为MC_5H_3N[CH=NN=C(S)XR]_2(M=VO~(2 )、Mn~(2 )和Fe~(2 ))和FeC_5H_3N[CH=NN=C(S)SR]_2Cl的希夫碱配合物。希夫碱及其配合物为元素分析、红外、可见一紫外光谱以及磁化率测量所表征,结果与所提出的Mn~(2 )、Fe~(2 )及Fe~(3 )配合物的结构一致.在VO(Ⅱ)配合物的情况,则形成多聚体,其结构为: -(N_3S_2)V-O-V(N_3S_2)-O-V(N_3S_2)-. 相似文献
11.
Zhang K Zhang W Wang S Sheng E Yang G Xie M Zhou S Feng Y Mao L Huang Z 《Dalton transactions (Cambridge, England : 2003)》2004,(7):1029-1037
The interaction of methoxyethyl functionalized indene compounds (C(9)H(6)-1-R-3-CH(2)CH(2)OMe, R =t-BuNHSiMe(2)(1), Me(3)Si (2), H (3)) with [(Me(3)Si)(2)N](3)Ln(mu-Cl)Li(THF)(3)(Ln=Yb (4), Eu (5)) produced a series of new ytterbium(II) and europium(II) complexes via tandem silylamine elimination/homolysis of the Ln-N (Ln=Yb, Eu) bond. Treatment of the lanthanide(III) amides [(Me(3)Si)(2)N](3)Ln(mu-Cl)Li(THF)(3)(Ln=Yb (4), Eu (5) with 2 equiv. of, 1,2 and 3, respectively, produced, after workup, the ytterbium(II) complexes [eta5:eta1-Me(2)Si(MeOCH(2)CH(2)C(9)H(5))(NHBu-t)](2)Yb(II) (6), (eta5:eta1-MeOCH(2)CH(2)C(9)H(5)SiMe(3))(2)Yb(II) (7), (eta5:eta1-MeOCH(2)CH(2)C(9)H(6))(2)Yb(II)(8) and the corresponding europium(II) complexes [eta5:eta1-Me(2)Si(MeOCH(2)CH(2)C(9)H(5))(NHBu-t)](2)Eu(II)(9), (eta5:eta1-MeOCH(2)CH(2)C(9)H(5)SiMe(3))(2)Eu(II)(10) and (eta5:eta1-MeOCH(2)CH(2)C(9)H(6))(2)Eu(II)(11) in moderate to good yield. In contrast, interaction of the corresponding indene compounds 1, 2 or 3 with the lanthanide amides [(Me(3)Si)(2)N](3)Ln (Ln = Yb, Eu) was not observed, while addition of 0.5 equiv. of anhydrous LiCl to the corresponding reaction mixture produced, after workup, the corresponding ytterbium(II) or europium(II) complexes. All the new compounds were fully characterized by spectroscopic and elemental analyses. The structures of complexes, and were determined by single-crystal X-ray analyses. The catalytic activity of all the ytterbium(II) and europium(II) complexes on MMA polymerization was examined. It was found that all the ytterbium(II) and europium(II) complexes can function as single-component MMA polymerization catalysts. The temperature, solvent and ligand effects on the catalytic activity were studied. 相似文献
12.
Matsumoto K Arai S Ochiai M Chen W Nakata A Nakai H Kinoshita S 《Inorganic chemistry》2005,44(23):8552-8560
Pentanuclear linear chain Pt(II,III) complexes [[Pt2(NH3)2X2((CH3)3CCONH)2(CH2COCH3)]2[PtX'4]].nCH3COCH3 (X = X' = Cl, n = 2 (1a), X = Cl, X' = Br, n = 1 (1b), X = Br, X' = Cl, n = 2 (1c), X = X' = Br, n = 1 (1d)) composed of a monomeric Pt(II) complex sandwiched by two amidate-bridged Pt dimers were synthesized from the reaction of the acetonyl dinuclear Pt(III) complexes having equatorial halide ligands [Pt2(NH3)2X2((CH3)3CCONH)2(CH2COCH3)]X' ' (X = Cl (2a), Br (2b), X' ' = NO3-, CH3C6H4SO3-, BF4-, PF6-, ClO4-), with K2[PtX'4] (X' = Cl, Br). The X-ray structures of 1a-1d show that the complexes have metal-metal bonded linear Pt5 structures, and the oxidation state of the metals is approximately Pt(III)-Pt(III)...Pt(II)...Pt(III)-Pt(III). The Pt...Pt interactions between the dimer units and the monomer are due to the induced Pt(II)-Pt(IV) polarization of the Pt(III) dimeric unit caused by the electron withdrawal of the equatorial halide ligands. The density functional theory calculation clearly shows that the Pt...Pt interactions between the dimers and the monomer are made by the electron transfer from the monomer to the dimers. The pentanuclear complexes have flexible Pt backbones with the Pt chain adopting either arch or sigmoid structures depending on the crystal packing. 相似文献
13.
Ochiai M Lin YS Yamada J Misawa H Arai S Matsumoto K 《Journal of the American Chemical Society》2004,126(8):2536-2545
Reaction of the platinum(III) dimeric complex [Pt(2)(NH(3))(4)((CH(3))(3)CCONH)(2)(NO(3))(2)](NO(3))(2) (1), prepared in situ by the oxidation of the platinum blue complex [Pt(4)(NH(3))(8)((CH(3))(3)CCONH)(4)](NO(3))(5) (2) with Na(2)S(2)O(8), with terminal alkynes CH[triple bond]CR (R = (CH(2))(n)CH(3) (n = 2-5), (CH(2))(n)CH(2)OH (n = 0-2), CH(2)OCH(3), and Ph), in water gave a series of ketonyl-Pt(III) dinuclear complexes [Pt(2)(NH(3))(4)((CH(3))(3)CCONH)(2)(CH(2)COR)](NO(3))(3) (3, R = (CH(2))(2)CH(3); 4, R = (CH(2))(3)CH(3); 5, R = (CH(2))(4)CH(3); 6, R = (CH(2))(5)CH(3); 7, R = CH(2)OH; 8, R = CH(2)CH(2)OH; 9, R = (CH(2))(2)CH(2)OH; 10, R = CH(2)OCH(3); 11, R = Ph). Internal alkyne 2-butyne reacted with 1 to form the complex [Pt(2)(NH(3))(4)((CH(3))(3)CCONH)(2)(CH(CH(3))COCH(3))](NO(3))(3) (12). These reactions show that Pt(III) reacts with alkynes to give various ketonyl complexes. Coordination of the triple bond to the Pt(III) atom at the axial position, followed by nucleophilic attack of water and hydrogen shift from the enol to keto form, would be the mechanism. The structures of complexes 3.H(2)O, 7.0.5C(3)H(4)O, 9, 10, and 12 have been confirmed by X-ray diffraction analysis. A competitive reaction between equimolar 1-pentyne and 1-pentene toward 1 produced complex 3 and [Pt(2)(NH(3))(4)((CH(3))(3)CCONH)(2)(CH(2)CH(OH)CH(2)CH(2)CH(3))](NO(3))(3) (14) at a molar ratio of 9:1, suggesting that alkyne is more reactive than alkene. The ketonyl-Pt(III) dinuclear complexes are susceptible to nucleophiles, such as amines, and the reactions with secondary and tertiary amines give the corresponding alpha-amino-substituted ketones and the reduced Pt(II) complex quantitatively. In the reactions with primary amines, the once formed alpha-amino-substituted ketones were further converted to the iminoketones and diimines. The nucleophilic attack at the ketonyl group of the Pt(III) complexes provides a convenient means for the preparation of alpha-aminoketones, alpha-iminoketones, and diimines from the corresponding alkynes and amines. 相似文献
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Mao Jiang-Gao Huang Jin-Shun Ma Jian-Fang Ni Jia-Zuan 《Transition Metal Chemistry》1997,22(3):277-280
The reaction of diglycolic acid, O(CH2CO2H)2, with Cu(NO3)2·2H2O and lanthanoid nitrate hydrate produces a series of novel Ln–Cu mixed metal complexes, [Ln2Cu3{O(CH2CO2)2}6]·nH2O (Ln=La, Nd, n=9; Ln=Er, n=6), which have been characterized by elemental analysis, i.r. spectroscopy, magnetic measurements and X-ray crystallography. The Ln3+ and Cu2+ ions are connected by the carboxylate groups of the ligands, resulting in the formation of a complicated network. 相似文献
16.
Jiménez MV Sola E Egea MA Huet A Francisco AC Lahoz FJ Oro LA 《Inorganic chemistry》2000,39(21):4868-4878
The course of methyl iodide oxidative addition to various nucleophilic complexes, [Ir2(mu-1,8-(NH)2naphth)(CO)2(PiPr3)2] (1), [IrRh(mu-1,8-(NH)2naphth)(CO)2(PiPr3)2] (2), and [Rh2(mu-1,8-(NH)2naphth)(CO)2(PR3)2] (R = iPr, 3; Ph, 4; p-tolyl, 5; Me, 6), has been investigated. The CH3I addition to complex 1 readily affords the diiridium(II) complex [Ir2(mu-1,8-(NH)2naphth)I(CH3)(CO)2(PiPr3)2] (7), which undergoes slow rearrangement to give a thermodynamically stable stereoisomer, 8. The reaction of the Ir-Rh complex 2 gives the ionic compound [IrRh(mu-1,8-(NH)2naphth)(CH3)(CO)2(PiPr3)2]I (10). The dirhodium compounds, 3-5, undergo one-center additions to yield acyl complexes of the formula (Rh2(mu-1,8-(NH)2naphth)I(COCH3)(CO)(PR3)2] (R = iPr, 12; Ph, 13; p-tolyl, 14). The structure of 12 has been determined by X-ray diffraction. Further reactions of these Rh(III)-Rh(I) acyl derivatives with CH3I are productive only for the p-tolylphosphine derivative, which affords the bis-acyl complex [Rh2(mu-1,8-(NH)2naphth)(CH3CO)2I2(P(p-tolyl)3)2] (15). The reaction of the PMe3 derivative, 6, allows the isolation of the bis-methyl complex [Rh2(mu-1,8-(NH)2naphth)(mu-I)(CH3)2(CO)2(PMe3)2]I (16a), which emanates from a double one-center addition. Upon reaction with methyl triflate, the starting materials, 1, 2, 3, and 6, give the isostructural cationic methyl complexes 9, 11, 17, and 18, respectively. The behavior of these cationic methyl compounds toward CH3I, CH3OSO2CF3, and tetrabutylamonium iodide is consistent with the role of these species as intermediates in the SN2 addition of CH3I. Compounds 18 and 17 react with an excess of methyl triflate to give [Rh2(mu-1,8-(NH)2naphth)(mu-OSO2CF3)(CH3)2(CO)2(PMe3)2][CF3SO3] (19) and [Rh2(mu-1,8-(NH)2naphth)(OSO2CF3)(COCH3)(CH3)(CO)(PiPr3)2][CF3SO3] (20), respectively. Upon treatment with acetonitrile, complexes 17 and 18 give the isostructural cationic acyl complexes [Rh2(mu-1,8-(NH)2naphth)(COCH3)(NCCH3)(CO)(PR3)2][CF3SO3] (R = iPr, 21; Me, 22). A kinetic study of the reaction leading to 21 shows that formation of these complexes involves a slow insertion step followed by the fast coordination of the acetonitrile. The variety of reactions found in this system can be rationalized in terms of three alternative reaction pathways, which are determined by the effectiveness of the interactions between the two metal centers of the dinuclear complex and by the steric constraints due to the phosphine ligands. 相似文献
17.
New ketonylplatinum(III) dinuclear complexes [Pt(2)((CH(3))(3)CCONH)(2)(NH(3))(4)(CH(2)COPh)](NO(3))(3) (4), [Pt(2)((CH(3))(3)CCONH)(2)(NH(3))(4)(CH(CH(3))COC(2)H(5))](NO(3))(3) (5), and [Pt(2)((CH(3))(3)CCONH)(2)(NH(3))(4)(CH(2)COCH(2)COCH(3))](NO(3))(3) (6) were prepared by treatment of platinum blue complex [Pt(4)(NH(3))(8)((CH(3))(3)CCONH)(4)](NO(3))(5) (2) with acetophenone, 3-pentanone, and acetylacetone, respectively, in the presence of concentrated HNO(3). The structures of complexes 4 and 6 have been confirmed by X-ray diffraction analysis, which revealed that the C-H bonds of the methyl groups in acetophenone and acetylacetone have been cleaved and Pt(III)-C bonds are formed. Formation of diketonylplatinum(III) complex 6 provides a novel example of the C-H bond activation not at the central alpha-C-H but at the terminal methyl of acetylacetone. Reaction with butanone having unsymmetrical alpha-H atoms led to two types of ketonylplatinum(III) complexes [Pt(2)((CH(3))(3)CCONH)(2)(NH(3))(4)(CH(CH(3))COCH(3))](NO(3))(3) (7a) and [Pt(2)((CH(3))(3)CCONH)(2)(NH(3))(4)(CH(2)COCH(2)CH(3))](NO(3))(3) (7b) at a molar ratio of 1.7 to 1 corresponding to the C-H bond activation of methylene and methyl groups, respectively. Use of 3-methyl-2-butanone instead of butanone gave complex [Pt(2)((CH(3))(3)CCONH)(2)(NH(3))(4)(CH(2)COCH(CH(3))(2))](NO(3))(3) (8) as a sole product via C-H bond activation in the alpha-methyl group. The reactivity of the ketonylplatinum(III) dinuclear complexes toward nucleophiles, such as H(2)O and HNEt(2), was examined. The alpha-hydroxyl- and alpha-amino-substituted ketones were generated in the reactions of [Pt(2)((CH(3))(3)CCONH)(2)(NH(3))(4)(CH(2)COCH(3))](NO(3))(3) (1), 5, and a mixture of 7a and 7b with water and amine, which indicates that the carbon atom in the ketonyl group bound to the Pt(III) atom can receive a nucleophilic attack. The high electrophilicity of the ketonylplatinum(III) complexes can be accounted for by the high electron-withdrawing ability of the platinum(III) atom. A competition between the radical and electrophilic displacement pathways was observed directly in the C-H bond activation reaction with butanone giving complexes 7a and 7b. Addition of a radical trapping agent suppressed the radical pathway and gave complex 7b as the predominant product. On the contrary, 7a was formed as the main product when the reaction solution was irradiated by mercury lamp light. These results together with other mechanistic studies demonstrate that complex 7a was produced via a radical process, whereas complex 7b is produced via electrophilic displacement of a proton by the Pt(III) atom. The competitive processes were further observed in the reactions of platinum blue complex 2 with a mixture of acetone and 3-pentanone in the presence of HNO(3). The relative molar ratio of acetonyl complex 1 to pentanoyl complex 5 was 3 to 1 under room light, whereas formation of complex 5 was almost suppressed when the reaction was carried out in the dark with the addition of a radical trapping agent. 相似文献
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19.
《结构化学》1992,(5)
<正> The title complexes were synthesized and their crystal structures were determined. These complexes crystallize in trigonal space group R3 with 3 molecules in a unit cell and are isostructural to each other. Crystallographic data: complex 1, Nd(CH3CONHCH2COO)3(H2O)3, Mr = 546. 6, a= 16. 582(4), c = 5. 982(2)(?), V= 1424. 5(8)(?)3, Dc=1. 91gcm-3, F (000) = 819, μ = 28.06cm-1, R(Rw) = 0. 048(0. 061); complex 2, Eu (CH3CONHCH2COO)3 (H2O)3, Mr = 554.3, a = 16.564(10), c=5.974(3)(?), V = 1418(2)(?)3,Dc= 1. 95gcm-3, R (Rw) = 0. 018 (0. 025), F (000) = 828, μ= 33. 83cm-1; complex 3, Er-(CH3CONHCH2COO)3(H2O)3, Mr = 569. 6, a = 16. 476(7), c=5. 946(6)(?), V = 1398(2) (?)3, D, = 2. 03gcm-3, R (Rw ) = 0. 020 (0. 027) , F (000) = 843, μ= 46. 25cm-1. These complexes adopt mononuclear structure, in which Ln(Ⅲ) ion is coordinated to six oxygen atoms from three ligands and three oxygen atoms from water molecules with the polyhedron of 4,4,4-tricapped triangular prism. The carboxy-lato group of the ligand bonds to Ln 相似文献