[Na·6THF][Cp_3Nd(μ-H)NdCp_3]·2THF配合物的合成与分子结构

Rossmanith报导,无水NdCl_3和萘锂在THF溶液中可生成NdCl_2·2THF。我们在研究这一类型化合物时考察了NdCl_3·2THF和CpNa(Cp为环戊二烯)在THF中的反应,分离出一种氢化物——[Na·6THF][Cp_3Nd(μ-H)NdCp_3]·2THP。这个配合物性能非常活泼,可以与含活泼氢的有机化合物作用使C-C及C-H键断裂。本文报导此配合物的合成及其分子结构,应当指出,1986年Schumann等人曾合成[Na·6THF][Cp3Lu(μ-H)LuCp3]·2THF,发现该配合物极不稳定,无法进行元素分析,对H桥的特征吸收峰亦未进行确切的归属。本文的标题化合物也有同样的问题。     

配合物[Fe(OPPh3)4Cl2][FeCl4]的合成和晶体结构

亚砜（R2SO4）是四价有机硫化合物中最重要的一类化合物,它的还原产物R2S可作为配体与过渡金属离子配位,从而得到许多结构新颖的化合物。这类反应一般在金属离子Os^11、Ru^11、Pt^11和Re^Vi等存在下发生,但很少出现在Fe^Ⅲ离子上。本文首次利用FeCl3、PPh3和DMSO反应,得到标题配合物并测定了其晶体结构。     

配合物Nd(C7H7N2O2)3(H2O)3的合成及其晶体结构

用水热法合成了3,5-二氨基苯甲酸与Nd(Ⅲ)的配合物Nd(C7H7N2O2)3(H2O)3(1),其结构经IR,元素分析和X-射线单晶衍射仪表征。1为单核结构,属六方晶系,R3空间群,晶胞参数:a=1.887 29(18)nm,b=1.887 29(18)nm,c=0.603 53(12)nm,β=90,°γ=120°,V=1.861 7(4)nm3,Z=3,μ=2.154 mm-1,Dc=1.744 g.cm-3,R1=0.014 3,wR2=0.033 2。1中Nd(Ⅲ)与来自3个3,5-二氨基苯甲酸的6个氧原子及3个配位水的氧原子进行配位,形成9配位化合物。     

氮杂大环钕配合物[Nd(L)(CH~3CN)(CF~3sO~3)~3]的合成和结构

本文报道了三价钕与氮杂大环(简称L)配合物的合成和晶体结构.配合物组成为[Nd(L)-(CH_3CN)(CF_3SO_3)_3],晶体属于三斜晶系,空间群为PI,晶胞参数α=0.8738(2),b=1.2870(3),c=1.2900(3)nm;α=85.63(2),α=87.25(2),γ=78.30(2)°;最终偏差因子R=0.0370,R_w00385.配合物中钕为8配位,其配位多面体为扭曲的四方反棱柱体.     

四元配合物[Nd(C_4H_3OCOO)_2·NO_3·C_(10)H_8N_2]_2的合成与晶体结构

稀土羧酸配合物在萃取分离、杀菌、催化和发光材料等方面有广泛的应用[1]。将氮杂环双齿配位体引入到这类配合物中可增强配合物的共轭作用,提高稳定性并增强其杀菌能力和发光性质[2]。虽然氮杂环双齿配位体邻菲咯啉的稀土羧酸配合物报道较多,但含2,2′联吡啶配位的稀土羧酸配合物的研究相对较少,尤其是含2,2′联吡啶的四元稀土羧酸混配配合物的研究更为少见[3]。2呋喃甲酸是糠醛在人体中的代谢产物,可做为防腐剂、熏蒸剂等,本文报道[Nd(C4H3OCOO)2·NO3·C10H8N2]2配合物的合成和单晶X射线衍射分析结果。2呋喃甲酸(分析纯)、2,2′联吡…     

[Nd(4-PYA)3(H2 O)2]n的合成及其晶体结构

3-(4-吡啶基)丙烯酸(4-HPYA)和Nd(NO3)3通过水热法合成了一种新的一维链状配位聚合物[Nd(4-PYA)3(H2O)2]n(1),其结构经IR,元素分析和X-射线单晶衍射表征。1属三斜晶系,P-1空间群,晶胞参数:a=0.829 23(13)nm,b=1.272 60(2)nm,c=1.435 00(12)nm,α=112.371(2)°,β=98.856(3)°,γ=100.239(2)°,V=1.336 6(3)nm3,Mr=660.72,Z=2,Dc=1.642 g.cm-3,F(000)=662,μ=2.002mm-1,R1=0.052 3,wR2=0.141 9。1通过分子间氢键作用将一维链紧密堆积成三维网状结构。     

稀土配合物[Nd(o-NO2-C6H4COO)3(DMF)2]2的合成及其晶体结构

合成了一种新的双核倒反中心的稀土钕配合物[Nd(o-NO₂-C₆H₄COO)₃(DMF)₂]₂. 通过元素分析, 核磁共振谱和红外光谱对配合物的组成和结构进行了表征, 用热重分析研究了该配合物的热稳定性, 用X射线单晶衍射法测定了其晶体的结构. 钕配合物[Nd(o- NO₂-C₆H₄COO)₃(DMF)₂]₂晶体属三斜晶系, 空间群P-1, 晶胞参数a＝1.18652(12) nm, b＝1.24784(13) nm, c＝1.29958(13) nm, α＝64.220 (1)°, β＝66.306 (1)°, γ＝71.825 (1)°, V＝1.5645 (3) nm³, D_c＝2.167 mg/m³, Z＝2, μ＝3.415 mm^－1, F(000)＝986. 配合物中每个Nd(Ш)被4个邻硝基苯甲酸根桥联, Nd(Ш)的配位数为8, 配位原子分别来自于5个邻硝基苯甲酸羧酸根的6个氧原子和2个DMF的羰基氧原子. 配合物中的氢键和π…π 堆积作用使其成为三维立体结构. 同时发现了标题配合物固体具有光致发光现象, 发光性能测试表明该配合物具有很好的荧光性质.     

钕缔合物[Nd(dmso)7Cl][BPh4]2的合成和晶体结构

在丙酮 /乙醇有机溶剂中合成了标题化合物 ,[Nd(dmso) 7Cl][BPh4 ]2 (dmso =二甲亚砜 ;BPh4 =四苯基硼离子 )并用单晶X射线四圆衍射分析测定了它的晶体结构。该晶体属三斜晶系 ,P1空间群 ,晶胞参数 :a =1 2 554(1)cm ,b =1 2 799(1)nm ,c =2 4 598(3)nm ,α =93 53(1)° ,β =10 4 50(1)° ,γ =112 77(1)° ,V =3 4 72 2 (6 )nm3,Z =2 ,Mr=136 5 0 1,Dc=1 30 6g·cm- 3,每个分子中含有一个配位阳离子 [Nd(dmso) 7Cl] 和两个平衡阴离子 [BPh4 ]。来自 7个亚砜配体的亚磺酰基氧原子和一个氯离子与稀土钕配位 ,形成一畸变的四方反棱柱大阳离子配位多面体。四苯硼酸根仅作为平衡电荷的大阴离子 ,不参与成键。     

双核银配合物Ag_2[Ph_2P(CH_2)_2Ph_2]_4(NO_3·CH_3OH)_2的合成和分子结构研究

dppe配体按文献所示方法自行合成。在10ml甲醇中先后溶入0.05g(0.29mmol)AgNO_3和0.23g(0.58mmol)dppe。将过滤后的清液半敞开静置14天,即析出棱形无色晶体,再以甲醇重结晶。晶体由于溶剂化而极易风化成白色粉末。     

配合物[Li(THF)_2]_2(μ—Cl)_4[(η~5—CH_3C_5H_4)Nd·THF]的合成及其晶体结构

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。     

SmCl3（DME）·2THF的晶体结构

我们曾测定NdCl_3·4THF的晶体结构,并研究了它对双烯烃聚合的活化作用.本文报导含二甲氧基乙烷(Dimethoxyethane,简称DME)的SmCl_3(DME)·2THF的制备及其单晶结构,以利于对稀土催化双烯烃聚合反应机理作出更好的解释.     

Synthesis and Crystal Structure of Neodymium Complex with Glycine [Nd(Gly)(H_2O)_7]Cl_3

ＩｎｔｒｏｄｕｃｔｉｏｎＡｐｐｌｉｃａｔｉｏｎｏｆｔｈｅｒａｒｅｅａｒｔｈｃｏｍｐｏｕｎｄｓｈａｖｅｂｅｅｎｆｏｕｎｄｉｎｍｅｄｉｃｉｎｅａｎｄａｇｒｉｃｕｌｔｕｒｅ．Ｓｏｔｈｅｒｅｍａｙｂｅｒａｒｅｅａｒｔｈｃｏｍｐｏｕｎｄｓｉｎｐｅｐｔｉｄｅａｎｄｐｒｏｔｅｉｎｃｏｍｐｌｅｘｅｓ．Ｉｔｉｓｉｍｐｏｒｔａｎｔｔｏｕｎｄｅｒｓｔａｎｄｍｏｒｅｃｌｅａｒｌｙｔｈｅｂｏｎｄｉｎｇｏｆｔｈｅｌａｎｔｈａｎｉｄｅｉｏｎｓｉｎｔｈｅｃｏｏｒｄｉｎａｔｉｏｎｃｏｍｐｏｕｎｄｓｗｉｔｈａｍｉｎｏａｃｉｄｓ．Ｓ…     

Li(THF)2(μ-Cl)2YCl2(THF)2的晶体和分子结构

配合物Li(THF)_2(μ-Cl)_2YCl_2(THF)_2,M=526.10,结构已由X射线衍射法测定,空间群C_2/c,a=21.333(5),b=10.371(10),c=22.559(4)(?),β=90.87(1)°,V=4990.4(?)~3,Z=8,μ(Cu K_a)=75.378cm~(-1),F(000)=2160,R=0.073。     

SYNTHESIS AND X-RAY CRYSTAL STRUCTURE OF THE CHLORIDE-BRIDGED FACE-SHARING BIOCTAHEDRAL DIRHODIUM COMPLEX [HP-i-Pr3][Rh2Cl7(P-i-Pr3)2]

Abstract

The reaction of an ethanolic suspension of [NH₄]₃RhCl₆] and P-i′-Pr₃, in the presence of concentrated HC1, for 24h, gives [HP-i-Pr₃][Rh₂Cl₇(P-i-Pr₃)₂], 1, in 18.5% yeild and a small amount of Rh(H)(Cl)₂(P-i-Pr₃)₂, 2. The dinuclear complex 1 was characterized by elemental analyses, IR, ¹H, ³¹P NMR spectroscopy, and single crystal X-ray analysis. However, when the above reaction is continued for 48 h one obtains only 2, in good yield. It is proposed that complex 1 is a reaction intermediate leading to 2. Crystallographic data for 1 (at 298 K) are a = 15.944(3), b = 22.413(4), c= 11.500(4) Å, space group Pna2_x (Z = 4).     

K2NdP2S7: A Mixed‐Valent Neodymium(III) Thiophosphate According to K4Nd2[PS4]2[P2S6] with Discrete [PS4]3– and [S3P–PS3]4– Anions

Pale blue, lath‐shaped single crystals of K₂NdP₂S₇ (≡ K₄Nd₂[PS₄]₂[P₂S₆]; monoclinic, P2₁/n, a = 904.76(8), b = 677.38(6), c = 1988.7(2) pm, β = 97.295(5)°, Z = 2) are obtained by the reaction of Nd, S and P₂S₅ with an excess of KCl as a flux in evacuated silica tubes at 750 °C (7 d) which should produce Nd[PS₄] instead. Beside isolated [PS₄]^3– tetrahedra, the crystal structure contains discrete ethane‐analogous [P₂S₆]^4– (≡ [S₃P–PS₃]^4–) units in staggered conformation with tetravalent phosphorus cations and a P–P distance of 219 pm. The two crystallographically different potassium cations show coordination numbers of nine and ten in the shape of distorted mono‐ and bicapped square antiprisms. Finally, the Nd³⁺ cations are surrounded by eight sulfur atoms arranged as (uncapped) square antiprisms. The entire structure is dominated by (K1)⁺ containing {(Nd₂[PS₄]₂[P₂S₆])^4–} layers parallel (101) which are three‐dimensionally interconnected by (K2)⁺ cations.     

A Tetrameric Neodymium Silanolate: [Nd(OSiMe3)3]4

The title compound [Nd(OSiMe₃)₃]₄ ( 1 ) was prepared by reaction of [Nd{N(SiMe₃)₂}₃] with Me₃SiOH in toluene at room temperature. Compound 1 crystallized from a concentrated toluene solution in the monoclinic space group P2₁/n with the lattice constants a = 15.144(1) Å, b = 25.142(1) Å, c = 20.391(1) Å and β = 103.755(2)°. In the solid state a tetramer is observed which shows Nd‐O bond distances in the range 2.129(2)‐2.675(2) Å.     

四核镨过氧根配位化合物〔Pr4(O2)2Cl8(THF)8(H2O)2〕·2THF的晶体和分子结构

本文用X—射线衍射法测定了[Pr_4(O_2)_2Cl(THF)(H_2O)_2]·2THF的晶体和分子结构。晶体属三斜晶系,空间群为Pi,晶胞参数为a=11.484(4),b=13.030(5),c=10.645(3)A,α=97.28(3),β=90.16(3),γ=102.84(3)°;Z=1。从三维Patterson函数分析结果确定独立的Pr和Cl原子座标,其余的全部非氢原子座际由若干轮Fourier和差Fourier合成中得到,最后的R因子为0.082。分子吴C点群对称性,其对称中心与晶体对称中心重合。四个中央Pr离子折氧化态为+3价,它们由氯桥和过氧根的“氧帽”联结在一起,构成含过氧帽的四核谱混合配位化合物。镨原子处于两种不同的化学环境,其配位数分别为8和9。     

SYNTHESIS AND CRYSTAL STRUCTURE OF[Li.4THF][GdCl_4·2THF]

GdCl_3 reacts with CH_3C_6H_4Li at a molar ratio of 2:1 in tetra-hydyofuran(THF)to yield an interesting compound [Li·4THF][GdCl_4·2THF];its X-ray crystal structure shows the molecule to be an ion-pair.     

Preparation and Crystal Structure of the Neodymium Borohydride [Li(thf)4]2[Nd2(μ‐Cl)2(BH4)6(thf)2]

The neodymium borohydride [Li(thf)₄]₂[Nd₂(μ‐Cl)₂(BH₄)₆(thf)₂] was synthesized from neodymium chloride and lithium borohydride. The compound crystallized in the triclinic crystal system, space group (No. 2) with the cell constants a = 14.8613(11), b = 17.8715(13), c = 23.5846(18) Å, α = 100.760(6), β = 90.648(6) and γ = 103.294(6)°. Each neodymium atom is coordinated by three borohydride anions and a THF molecule whereas two neodymium cations are bridged through two chloro ligands. The charge of the [Nd₂(μ‐Cl)₂(BH₄)₆(thf)₂]²⁻ anion, which represents the first structurally characterized binuclear mixed borohydride chlorido complex, is compensated by two [Li(thf)₄]⁺ cations.