三甲硅基环戊二烯基稀土二氯化物的合成

1978年Lappert等人首先合成了二(三甲硅基环戊二烯基)稀土氯化物[Li(THF)](Me_3SiC_5H_4)_2LnCl] (Ln=Y,Yb)和Yb(C_5H_4SiMe_3)_2。三甲硅基环戊二烯基稀土二氯化物,则未见报导.采用三甲硅基环戊二烯作为合成稀土金属有机化合物的配体,不仅可以增加所合成的稀土化合物在非极性溶剂中的溶解度,而且在反应过程中可以减小歧化反应的发生,得到所要求的产物.我们探索了三甲硅基环戊二烯基稀土二氯化物的合成,并对所得到的产物进行了鉴定.     

四氢糠基环戊二烯稀土氯化物的合成及表征

报道了四氢糖基环戊烯基稀土氯化物的合成，用元素分析，红外光谱，质谱和核磁共振谱表征这类化合物的组成为（Ｃ４Ｈ７ＣＯＨ２Ｃ５Ｈ４）２ＬｎＣ１（Ｌｎ＝Ｎｄ，Ｇｄ，Ｄｙ，Ｅｒ），测定了（Ｃ４Ｈ７ＯＣＨ２Ｃ５Ｈ４）２ＤｙＣｌ的晶体结构属正交晶系，Ｐ２，２１２１空间群，晶胞参数：α＝１．１８０９（３）ｎｍ，ｂ＝１．２１４９（４）ｎｍ，ｃ＝１．３３７７（５）ｎｍ，ｚ＝４，Ｄｃ＝１．７２ｇ／ｃｍ＾３，Ｒ＝０．０     

环戊烷基（或烯丙基）环戊二烯基稀土二氯化物的合成

本文报导环戊烷基(或烯丙基)环戊二烯基稀土二氯化物的合成。用元素分析,热分析、红外光谱、质谱和核磁共振谱表征了这两类化合物组成为C_5H_9C_5H_4LnCl_2·nTHF和C_3H_5C_5H_4LnCl_2·nTHF(Ln=Nd,Sm,Gd;n=0,1,2,3)测定了反应中间体C_5H_9C_5H_4Na·THF的晶体结构。     

1,1—二甲基—3—丁烯基环戊二烯基稀土二氯化物的合成

１，１－二甲基－３－丁烯基环戊二烯基稀土二氯化物的合成林进张萍王昭煜＊（河北师范大学化学系石家庄０５００１６）关键词烯基环戊二烯基，稀土二氯化物，配合物，合成１９９７－０８－０６收稿，１９９７－１２－０５修回河北省自然科学基金资助课题环戊二烯基轻稀土...     

桥联二芴基稀土氯化物的合成及表征

用二（9－芴基）二甲基硅烷（Me2SiFlu2）的双锂盐与三氯稀土在室下反应合成了5个通式为Me2SiFlu2LnCl(Ln=Yb,Sm,La,Pr,Nd）的桥联二芴基稀土氯化物，所有配合物均经元素分析、IR，MS和^1H NMR表征。     

1-甲基-1-丙基-3-丁烯基环戊二烯基稀土二氯化物的合成

丁烯基环戊二烯基稀土氯化物;1-甲基-1-丙基-3-丁烯基环戊二烯基稀土二氯化物的合成     

四氢糠基芴稀土氯化物的合成

采用无水无氧Schlenk法合成了一种新型芴基配体--四氢糠基芴(LH).LH与稀土氯化物反应制备了5个芴基稀土配合物,收率57%-73%,其结构经IR和元素分析表征.     

苯基稀土氯化物的合成及其表征

1970年,Hart等首先合成了Sc(C_6H_5)_3、Y(C_6H_5)_3、LiLa(C_6H_5)_4和LiPr(C_6H_5)_4。1972年,Cotton等测定了[Lu(2,6-(CH_3)_2C_6H_3)_4]·[Li·4THF]的晶体结构。1986年,陈文启等人合成了Nd(C_6H_5)_3,Gd(C_6H_5)_3和LiNd(C_6H_5)_4。本文首次合成了苯基稀土氯化物C_6H_5LnCl_2·nTHF(Ln=Pr,Sm,Gd,n=3,4);C_6H_5LnCl_2·LiCl·nTHF(Ln=Pr、Nd、Sm、Gd,n=2、3、5);(C_6H_5)_2GdCl·LiCl·2THF;[(C_6H_5)_2NdCl]_2·LiCl·4THF。测定了C_6H_5GdCl_2·4THF的晶体结构。     

环戊二烯基轻稀土二氯化物邻菲罗啉配合物的合成

用LnCl~3邻菲绕啉和C~5H~5Na在四氢呋喃中的反应合成了四个1,10-二氮杂菲配位的含四氢呋喃的轻稀土环戊二烯二氯化物。用元素分析、红外光谱、电子能谱、差热分析等方法鉴定了这四个新化合物。     

若干环戊二烯基(N,N-二苄基氨荒酸)锆衍生物的质谱研究

本文通过电子轰击谱,并借助于同位素丰度分析和亚稳跃迁数据,阐述了标题衍生物(MeCp)Zr(S_2CN(C_7H_7)_2)_3(Ⅰ)、CpZr(S_2CN(C_7H_7)_2)_3(Ⅱ)、(MeCp)_2ZrCl(S_2CN(C_7H_7)_2)(Ⅲ)和Cp_2ZrCl(S_2CN(C_7H_7)_2)(Ⅳ)的质谱断裂途径。对于配合物(Ⅰ)和(Ⅱ),可看到从分子离子中首先丢失N,N-二苄基氨荒酸配体或该配体的部分碎片离子(C_7H_7~+),构成两个配合物的主要断裂途径。而丢失Cp或MeCp配体,在两种配合物质谱中则有差别。一般地说,Cp较MeCp易于丢失。这可能由于MeCp比Cp有较强给电子能力,因而使配体与金属间键得以加强。对于配合物(Ⅲ)和(Ⅳ),上述关系不明显。在配合物(Ⅳ)中,通过同位素丰度分析,指明m/z 462和m/z 463两种不同离子组成的两簇峰相互重叠,构成观察到的一簇叠加同位素峰。     

Organoamido- and aryloxo-lanthanoids. XIII [1]. Organometallic compounds of the lanthanoids. CV [2]. New Lanthanoid(III) Complexes with Pyrazolate Ligands

The complexes Er(Me₂pz)₃(thf) and Ln(Ph₂pz)₃(thf)_n (Ln = Sc, Y, Gd, Er, n = 2; Ln = Lu, n = 3) (Me₂pz^? = 3,5-dimethylpyrazolate, thf = tetrahydrofuran, Ph₂pz^? = 3,5-diphenylpyrazolate) have been prepared by reaction of the lanthanoid metal with bis(pentafluorophenyl)mercury and the pyrazole in thf. The Ln(Ph₂pz)₃(thf)₂ complexes are considered to be eight coordinate with three η²-Ph₂pz ligands. Other lanthanoid pyrazolate complexes, Y(pz)₃(thf)₂, La(Me₂pz)₃(thf), Cp₂Ln(Me₂pz)(thf)_n (Ln = Y, Lu, n = 0; Ln = Lu, n = 1), (C₅Me₅)₂Y(pz)(thf), (C₅Me₅)₂Y(Mepz)(thf), (C₅Me₅)₂Y(Me₂pz)(thf)₂ (pz^? = pyrazolate, Mepz^? = 3-methylpyrazolate, Cp = cyclopentadienyl) have been synthesized by reaction of LnCl₃, Cp₂LnCl, or (C₅Me₅)₂LnCl with the appropriate sodium pyrazolate in thf. The structure of Ln(Me₂pz)₃(thf) (Ln = La or Er) is considered to be a symmetrical dimer with four chelating and two bridging Me₂pz groups, and two bridging thf ligands, whereas the cyclopentadienyl complexes are most likely dimers with bridging pyrazolate groups, and lattice thf of solvation.     

大取代茂锆配合物合成及分子内消除反应研究

通过6,6-二烷基富烯与2-MeOArLi进行加成反应, 得到含芳氧取代的环戊二烯基锂盐, 再与取代茂三氯化锆反应, 合成了不对称大位阻取代茂锆配合物RCpCp^oZrCl₂ [Cp^o＝2-MeOArCR¹R²Cp, R¹, R²＝CH₃, C₂H₅, (CH₂)₅, etc.], 所得的配合物均通过¹H NMR, IR, MS和EA鉴定. 在此过程中发现该类配合物能进行分子内消除反应, 脱去苯甲醚得到烯基取代的二氯二茂锆配合物, 该反应为未见文献报道的新反应, 对该反应进行了研究.     

Lanthanoid Complexes as Molecular Materials: The Redox Approach

The development of molecular materials with novel functionality offers promise for technological innovation. Switchable molecules that incorporate redox-active components are enticing candidate compounds due to their potential for electronic manipulation. Lanthanoid metals are most prevalent in their trivalent state and usually redox-activity in lanthanoid complexes is restricted to the ligand. The unique electronic and physical properties of lanthanoid ions have been exploited for various applications, including in magnetic and luminescent materials as well as in catalysis. Lanthanoid complexes are also promising for applications reliant on switchability, where the physical properties can be modulated by varying the oxidation state of a coordinated ligand. Lanthanoid-based redox activity is also possible, encompassing both divalent and tetravalent metal oxidation states. Thus, utilization of redox-active lanthanoid metals offers an attractive opportunity to further expand the capabilities of molecular materials. This review surveys both ligand and lanthanoid centered redox-activity in pre-existing molecular systems, including tuning of lanthanoid magnetic and photophysical properties by modulating the redox states of coordinated ligands. Ultimately the combination of redox-activity at both ligands and metal centers in the same molecule can afford novel electronic structures and physical properties, including multiconfigurational electronic states and valence tautomerism. Further targeted exploration of these features is clearly warranted, both to enhance understanding of the underlying fundamental chemistry, and for the generation of a potentially important new class of molecular material.     

二氯二苯基锡与单核苷酸配位作用的研究

研究了二氯二苯基锡（Ｐｈ＿２ＳｎＣｌ＿２）与核酸的基本组成单元──单核苷酸在水相中的配位作用，并用热分析、傅利叶变换红外光谱和￣１Ｈ、￣（３１）Ｐ超导核磁共振谱对新配合物Ｐｈ＿２Ｓｎ（５＇－ＡＭＰ）·Ｈ＿２Ｏ、Ｐｈ＿２Ｓｎ（５＇－ＣＭＰ）·Ｈ＿２Ｏ和Ｐｈ＿２Ｓｎ（５＇－ＧＭＰ）进行了详细的表征。结果表明，在配合物中锡仅与单核苷酸的磷酸根结合，给出了配合物的可能结构。     

Syntheses and Crystal Structures of Benzyl-and Cyclopentyl-Cyclopentadienyl Sodium Tetrahydrofuranate Complexes

The present paper covers syntheses and crystal structures of benzyl- and cy-clopentyl-cyclopentadienyl sodium tetrahydrofuranate complexes C6H5CH2C5H4Na·THF (1) and C5H9C5H4Na°THF (2). X-ray diffraction data of the title compounds were collected at a low temperature (about 210K). Structures of both the crystals belong to monoclinic space group P21/n with α=0. 9316(3) nm, b=1. 5161(4) nm, c= 0.9791(3) nm, β=91. 06(3)°Z=4 for (1) and α=1. 6120(7) nm, b=0. 9370(3) nm, c=1. 8475(7) nm, β=109.52(3)°Z = 8 for (2). Both structures were solved by using direct methods and refined by block-matrix least-squares to final values of R = 0. 044 for 520 observed reflections (1) and R = 0. 067 for 921 observed reflections (2). In the crystals the tetrahydrofuranate complexes C6H5CH2C5H4Na·THF and C5H9C5H4Na·THF adopt a puckered chain structure with η5-(C6H5CH2)C5H4 and η5-(C5H9)C5H4 rings connected by a bridge Na (THF) unit.     

二氯二茂锆取代芳肟的合成与结构

二氯二茂锆与等当量的各种芳肟的钠盐在二氯甲烷中反应，得到１０种二氯二茂锆取代衍生物，均为新化合物。这些化合物对水、空气和光敏感，稳定性差。对它们的合成及ＩＲ，＾１ＨＮＭＲ进行了初步讨论。     

二苄基二氯化锡三苯基氧膦的合成及晶体结构研究

利用二苄基二氯化锡与三苯基氧膦反应 ,合成了目标化合物二苄基二氯化锡三苯基氧膦 ,其结构经元素分析表征。用X 射线单晶衍射测定其晶体结构属于三方晶系 ,空间群为P2 1,a =2 .0 2 7( 4 )nm ,b =0 .9714 ( 17)nm ,c =1.5 5 9( 3)nm ,α =90° ,β =90° ,γ =90° ,Z =4 ,V =3.0 4 9( 10 )nm3 ,Dc =1.4 0 7mg·m-3 ,u =1.0 81mm-1,F( 0 0 0 )=1312 ,R1=0 .0 370 ,wR2 =0 .0 6 88,晶体中心的Sn原子为五配位的畸变三角双锥构型     

二(对-氯苄基)二氯化锡的合成及晶体结构

用 X射线方法测定了二 (对氯苄基 )二氯化锡的晶体结构,该化合物晶体属单斜晶系,空间群为 C2/c,晶体学参数： a=2.8010(3), b=0.4882(2), c=1.2174(3)nm,β =111.71(1)°, V=1.5467(7) nm3, Z=4, Dx=1.893g· cm－ 3,μ (MoKα )=23.24cm－ 1, F(000)=856.00, R=0.025, Rw=0.038, Sn C键长为 0.2148(3)nm, Sn Cl键长为 0.23754(9)nm。空间构型为畸变四面体构型的单分子有机锡化合物。