Convenient Synthesis of N-Trimethylsilylaminotitanium Trichlorides

Bis(N-trimethylsilylamino)plumbylenes 1 {[Me₃Si(R)N]₂Pb with R = ^tBu ( a ), Me₃Si ( b ), 9-(9-borabicyclo[3.3.1]nonyl) ( c )} react smoothly with an excess of TiCl₄ to give PbCl₂ and N-trimethylsilylaminotitanium trichlorides 3 a – c . In contrast, the analoguous reaction of the corresponding stannylenes 2 a – c leads to mixtures containing unidentified Ti^III compounds, the amides 3 a or 3 b , bis[bis(trimethylsilyl)amino]titanium dichloride 4 b and bis(amino)tin dichlorides 5 a – c . The crystal structure of 3 a was determined by X-ray structural analysis. Compound 3 a is a dimer in the solid state with distorted trigonal pyramidal surroundings of the titanium atoms. Each titanium atom bears two μ²-Cl ligands which are in axial (d_Ti–Cl = 250.7(1) pm) and equatorial positions (d_Ti–Cl = 247.0(1) pm) and two terminal chloro ligands, one in axial (d_Ti–Cl = 228.0(1) pm) and one in equatorial position (d_Ti–Cl = 221.1(1) pm). The equatorial Ti–N bonds are short (183.8(2) pm).     

Synthesis and Structure of Complexes of the Diethyl Ester of 2-Dimethylamino-2-oxoethylphosphonic Acid with Lanthanide Nitrates

The lanthanide complexes LnL 2 (NO 3 ) 3 ( 3a-g ) are obtained where Ln is La, Sm, Yb, Er, Ce, Eu, Gd, and L is the diethyl ester of 2-dimethylamino-2-oxoethylphosphonic acid [(C 2 H 5 O) 2 P(O)CH 2 CON(CH 3 ) 2 ] 1 . They are characterized by elemental analysis, i.r. and NMR spectroscopy. The crystal structure of 3a is determined by single crystal X-ray diffraction. The complex is found to crystallize in the triclinic space group P 1 with a = 8.4220(17) Å, b = 11.123(2) Å, c = 17.560(4) Å, f = 87.20(3);, g = 82.27(3);, n = 76.89(3);, V = 1587.3(5) Å 3 , Z = 2, calcd = 1.614 mg/m 3 , R = 0.047, R w = 0.107, S = 1.034 for 5762 reflections with I > 2 (I). The structure contains monomeric units of the complex with the lanthanum atom coordinated by 10 oxygen atoms, six of them from the three bidentate nitrate ions and four from the two phosphonate ligands. The coordination is realized by both phosphoryl and amide-carbonyl oxygen atoms. The stereochemistry of the starting ligand 1 is investigated by NMR spectroscopy.     

Synthesis, Structure and Transesterification of the Derivatives of b -Alkoxycarbonylethyltin Trichlorides with Diethyldithiocarbamate

The derivatives of b -alkoxycarbonylethyltin trichlorides with diethyldithiocarbamate, ROCOCH2CH2Sn(S2CNEt2)Cl2, were synthesized and characterized by the means of elemental analysis, IR, 1H NMR and X-ray single crystal diffraction. The structural features of the compounds were described, and the possible mechanism of transesterification for compound 2a was suggested.     

喹喔啉—2,3—二甲酰胺与3d过渡金属配合物的合成及性质研究

首次合成了喹喔啉－２，３－二甲酰胺（Ｑｘｄａ）与３ｄ过渡金属的三种固体配合物：Ｍ（Ｑｘｄａ）２ｃｌ２（Ｍ＝Ｃｏ（Ｉ），Ｎｉ（Ｉ），Ｃｕ（Ⅱ）。通过元素分析，摩尔电导，红外光谱，电子光谱，磁化率，热分析等手段对配合物的组成和性质进行了研究。     

1,2-二(2-胺基苯氧基)乙烷银配合物的合成与晶体结构

本文采用配体1, 2-二(邻氨基苯氧基)乙烷(L)分别与AgPF6, AgCF3SO3, AgNO3和AgSbF6 进行配位反应,依次得到了四个配合物1 [Ag2(L)2(PF6)]、2 [Ag2(L)2(CF3SO3)2]、3 [Ag(L)NO3]n 和4 [Ag(L)2SbF6]n,并通过FTIR、元素分析、以及X射线单晶衍射等对配合物的结构与组成进行了表征。单晶衍射结果表明,配合物1和2为双核银(I)配合物,3和4为银(I)的配位聚合物。配合物1具有穴状结构,2经Ag?Ag键桥连两个配体形成扭曲的非平面结构。聚合物3的结构为一维(1D)“之”字链,4具有三维(3D)多孔的结构框架。在四个配合物结构中,相应的抗衡阴离子均未参与Ag(I)进行配位作用。     

Programmable Oligonucleotide-Peptide Complexes:Synthesis and Applications

Nucleic acids form biological blueprint and polypeptides assist life activities, both of which are indispensable to organisms. Recently, oligonucleotide-peptide complexes (OPCs) have shown great potential in biomedicine, material chemistry and other fields due to their considerable stability and programmability. It remains a huge challenge to stably and facilely constructing OPCs that also limits the wide applications. This tutorial review first summarizes the synthesis strategies of OPC conjugation and the corresponding characteristics in detail, then gives examples of the applications of OPCs, and finally presents a prospective overview on challenges and future perspectives of OPCs. This review aims to help researchers understand the current situation and challenges in this field, thereby furthering interests in developing novel OPC synthesis techniques.     

二维含镧链异核金属化合物的合成、结构和磁性研究

水热法合成了3个层状异核金属化合物[Ln(idaH)M(ida)₂]_n·0.5nH₂O,(H₂ida=亚氨基二乙酸,Ln=Nd,M=Co (1);Ln=La,M=Co (2);Ln=La,M=Ni (3))。进行了晶体结构测定,红外光谱分析、能谱分析与磁性能分析。3个化合物除金属原子不同外具有相同的结构,其晶体都属于单斜晶系,C2/c空间群。单晶结构表明该结构含有由十配位的Ln通过羧基氧连接而成的链,六配位的3d金属(Co、Ni)交替地处在链的两边,形成了带状结构,带状链通过配体连成二维结构,通过氢键形成三维骨架。     

稀土硝酸盐与Cyclam离子缔合物的合成,性质及结构

在弱酸性介质中,以硝酸稀土与Cyclam在甲醇-水溶液中反应合成了La-Tb、Y9种离子缔合物。通过元素分析和IR、~1H NMR及DTA-TG研究,推测该类化合物的通式为;L~+L_(0.7)~(2+)·[Ln(NO_3)_6]_(0.8)[Ln(NO_3)_3·3H_2O]_(0.2)·nH_2O(La,Ce:n=3;Pr-Tb,Y:n=2.5,L为Cyclam)。经单晶四圆衍射结构分析,确定了化合物的晶体结构,晶胞参数为:a=1.7000(1)nm,b=1.7000(1)nm,c=1.9862(4)nm,α=β=90°,γ=120°,R3空间群,D_c=1.703g/cm~3,μ(K_a)=132.9cm~(-1)。     

某些稀土硝酸盐与N,N-二亚水杨基乙二胺-二甲基亚砜三元配合物的合成和晶体结构

合成了Tb(Ⅲ)、Y(Ⅲ)、Nd(Ⅲ)硝酸盐与N,N-二亚水杨基乙二胺、二甲基亚观的配合物[RE(C₆H₄OHCHNC₂H₄NCHC₆H₄OH)(NO₃)₃(CH₃SOCH₃)］.Tb(Ⅲ)配合物晶体为单斜晶系,空间群P2₁/n,a=0.9628(3)nm,b=1.6439(4)nm,C=1.6256(2)nm,β=102.78(2)°,V=2.509(2)nm₃,D_x=1.830g/cm³,Z=4,μ=2.996mm^-1,F(000)=1368,R=0.043,R_w=0.046.Tb(Ⅲ)的配位数是9,配位几何为单帽四方反核柱.所有的配位原子都是氧原子.两个中心离子被双Schiff碱桥联,形成一维无限长链.     

系列大环草酰胺配合物的合成与表征——推荐一个综合化学实验

采用加热回流和溶剂热两种方法合成了三种大环草酰胺系列配合物,并对所得配合物进行单晶结构解析。使用元素分析、红外光谱、电子光谱、ESR谱对配合物进行了表征和性质研究。该实验原料简单易得,实验方法简便易行,可操作性强,有利于培养学生的实践能力和创新能力。     

由MOPIP配体构筑的两种金属配合物的合成、表征及晶体结构(英文)

采用水热法由2种不同金属盐和MOPIP(MOPIP=2-(4-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline)配体合成了2种新型零维配合物[Cd(MOPIP)3(H2O)9]4n(1)和[Mn(MOPIP)3(H2O)6]2n(2),并对其进行了元素分析、红外光谱表征、热失重和X射线单晶衍射测定。结果表明,每个金属中心离子与来自3个不同MOPIP分子上的6个氮原子进行配位,形成畸变的八面体构型。     

镧系元素Dawson结构钨钒磷四元杂多配合物的合成、表征以及对H2O2分解的催化活性

合成了通式为K₁₅H₃[Ce(P₂W₁₆VO₆₁)₂]·61H₂O、K₁₅H₄[Ln(P₂W₁₆VO₆₁)₂]·xH₂O(Ln=La³⁺,Pr³⁺,Nd³⁺,Sm³⁺,Eu³⁺,Gd³⁺,Dy³⁺,Yb³⁺)的9种镧系元素Dawson结构的钨钒磷四元杂多配合物,并用IR、UV、NMR、ESR、XRD、TG-DTA等对其结构和性质进行了研究。该类配合物具有与K₁₆[Ce(P₂W₁₇VO₆₁)₂]·50H₂O类似的结构,对H₂O₂分解有较高的催化活性。     

Synthesis and Characterization of Chiral Organogallium and Indium Complexes with Salen Ligands

Several new chiral organogallium and indium complexes with chiral Salen(1 and 2) as anxciliary ligands have been synthesized and characterized by elemental analysis,IR,^1H NMR and Mass spectroscopy.For the gallium,Mono and bimetallic complexes were obtained,whereas ring closure complexes of indium were obtained.     

Synthesis and Structure of Co(III) Complexes with 2-Pyridinecarboxylic Acid

The Co(III) complexes with pyridinecarboxylic acid, Na[Co(Pc)₂(NO₂)₂] (I) and NH₄[Co(Pc)₂(NO₂)₂] (II), where Pc is the 2-pyridinecarboxylate anion, have been synthesized and studied by X-ray diffraction. In the crystal, the complex anions are combined through the Na⁺ and NH ₄ ⁺ cations. In II, the anion and the cation are combined by hydrogen bonds.     

Synthesis and Structure of Uranium-Silylene Complexes

While carbene complexes of uranium have been known for over a decade, there are no reported examples of complexes between an actinide and a „heavy carbene.“ Herein, we report the syntheses and structures of the first uranium-heavy tetrylene complexes: (CpSiMe₃)₃U-Si[PhC(NR)₂]R’ (R=tBu, R’=NMe₂ 1 ; R=iPr, R’=PhC(NiPr)₂ 2 ). Complex 1 features a kinetically robust uranium-silicon bonding interaction, while the uranium-silicon bond in 2 is easily disrupted thermally or by competing ligands in solution. Calculations reveal polarized σ bonds, but depending on the substituents at silicon a substantial π-bonding interaction is also present. The complexes possess relatively high bond orders which suggests primarily covalent bonding between uranium and silicon. These results comprise a new frontier in actinide-heavy main-group bonding.     

Synthesis and Structure of Hexachloroplatinate Complexes

The reactions of tetraorganylphosphonium and trimethylammonium chlorides with hexachloroplatinic acid hydrate in an acetonitrile–diethyl sulfoxide solution produced [Ph₃PCH=CHCH₃]₂[PtCl₆], [Ph₃PCH₂OCH₃]₂[PtCl₆], and [Me₃NH]₂[PtCl₆] complexes. The structure of the resultant platinum complexes was examined by X-ray diffraction analysis.

     

Synthesis and Structure of Borane Complexes with 3-Hydroxyflavone

Conclusions have been made regarding the structure of the complexes formed between flavonol and boranes of different structures on the basis of the analysis of their ¹H, ¹³C, and ¹¹B NMR spectra, IR and electronic spectra, and also from the results of quantum-chemical calculations. In all of the complexes, independently of the structure and acceptor properties of the boranes, it was found that the donor acceptor bond is formed between the boron atoms and the oxygen of the carbonyl group in the flavonol. Despite the lowered electron-donor ability of the carbonyl group oxygen atom after the formation of the bond to the boron atom it is likely that the hydrogen bond between the carbonyl and the 3-hydroxy group of the flavonol is retained. It was found that the carbonyl group of the flavonol has a lower electron-donor ability than the analogous group of aliphatic and aromatic ketones.     

1-甲基-2-咪唑醛肟锰(III)配合物的合成、晶体结构及电化学性质研究

采用溶剂扩散法获得了锰(III)的两个单核配合物 [Mn(Miao)2(H2O)2]ClO4(1)和[Mn(Miao)2(DMF)2]ClO4(2)（HMiao = 1-甲基-2-咪唑醛肟,DMF = N,N-二甲基甲酰胺）的晶体。X-射线衍射单晶结构表明：两种配合物均属三斜晶系,空间群Pī,锰与配位原子形成稳定的八面体结构。采用Gaussian03W程序计算了HMiao配体的电荷密度,理论计算与实际配位形式完全吻合。通过循环伏安法测定了两种锰配合物在DMF 溶液中的电化学性质。     

三苯基锡与邻氨基苯甲酸型Schif碱配合物的合成及表征

合成了两种新的三苯基锡与邻氨基苯甲酸型Ｓｃｈｉｆ碱的配合物，经元素分析、ＵＶ、ＩＲ、１ＨＮＭＲ测定，对其结构进行了表征。结果表明，两种配合物具有不同的结构。在三苯基锡与水杨醛缩邻氨基苯甲酸Ｓｃｈｉｆ碱的配合物中，锡原子是六配位的，存在着酚羟基氧和亚氨基氮与锡的配键。在三苯基锡与２－羟基－１－萘醛缩邻氨基苯甲酸Ｓｃｈｉｆ碱的配合物中，锡原子是五配位的，酚羟基氧和亚氨基氮均未与锡配位，但存在着羰基氧与锡的配键     

2-乙烯基噻吩-8-羟基喹啉锌的设计合成及光致发光特性研究

合成了2-[2-(5-溴代噻吩-2-基)-乙烯基]-8-羟基喹啉(1)和2-[2-(5'-溴代二噻吩-5-基)-乙烯基]-8-羟基喹啉(2)两个新化合物; 利用IR, UV, ¹H NMR, MS, 元素分析等确认其结构; 利用X射线单晶衍射仪测定了化合物1的晶体结构; 用MTT法评价了化合物1和2对鼠骨髓间质干细胞在不同浓度下的影响, 研究结果表明它们对鼠骨髓间质干细胞具有增殖作用. 化合物1和2与醋酸锌反应获得了其相应的锌配合物3和4, 光致发光显示: 它们的λ_max分别是597和620 nm.