顺式双氯[1,2-双(苯基硫代)乙烷]合铂(Ⅱ)的合成和结构

标题化合物PhS(CH_2)_2SPhPtCl_2,由Pt(Ⅳ)通过不稳定中间产物直接合成。配合物晶体属单斜晶系,空间群C_(2h)~5-P2_1/c。晶胞参数:a=9.735(1),b=10.056(1),c=14.718(2),β=101.07(1)°,V=1554.6,D_c=2.19g/cm~3,Z=4。分子为单核顺式四配位螯合结构,用姜-台勒效应讨论了分子构型的畸变。     

Molekülstruktur von 2,2-Bis(diisopropoxyphosphonyl)propyl-methylzinndibromid

Molecular Structure of 2,2-Bis(diisopropoxyphosphonyl)propyl Methyltin Dibromide By methylation of Me₃SnCH₂CH[P(O)(OPr?i)₂]₂ with NaH/MeI Me₃SnCH₂C(Me)[P(O)(OPr?i)₂]₂ ( 1 ) is obtained, which is converted by bromine into the dibromide MeBr₂SnCH₂C(Me)[P(O)(OPr?i)₂]₂ ( 2 ). An X-ray crystal structure analysis shows 2 to be monomeric. The tin atom is situated in the centre of a distorted octahedron, in which the functional substituent is intramolecular coordinated as tridentate ligand in a facial mode. The two organo groups are arranged in trans-position (C? Sn? C 155.1°), whereas the oxygen and bromine atoms are orientated cis to each other. The six-membered ring of the bicyclic molecular fragment of 2 which results from the coordination of the functional organo group to the tin atom shows a boat-conformation, whereas the two five-membered rings exist in twist-conformations. Multinuclear n.m.r. and i.r. data show that 2 retains its solid state structure also in nonpolar solvents.     

Mono- and diprotonation of the superbasic bisguanidine 1,2-Bis(N,N,N',N'-tetramethylguanidino)benzene (btmgb) and Pt II and Pt IV complexes of chelating bisguanidines and guanidinates

New Pt complexes of chelating bisguanidines and guanidinate ligands were synthesized and characterized. 1,2-Bis(N,N,N',N'-tetramethylguanidino)benzene (btmgb) was used as a neutral chelating bisguanidine ligand, and 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate (hpp(-)) as a guanidinate ligand. The salts [btmgbH](+)[HOB(C(6)F(5))(3)](-) and [btmgbH(2)]Cl(2) and the complexes [(btmgb)PtCl(2)], [(btmgb)PtCl(dmso)](+)[PtCl(3)(dmso)](-), and [(btmgb)PtCl(dmso)](+)[Cl(-)] were synthesized and characterized. In the [btmgbH](+) cation the proton is bound to only one N atom. In the other complexes, both imine N atoms are coordinated to the Pt(II), thus adopting a eta(2)-coordinational mode. The hpp(-) anion, which usually prefers a bridging binding mode in dinuclear complexes, is eta(2)-coordinated in the Pt(IV) complex [(eta(2)-hpp)(hppH)PtCl(2){N(H)C(O)CH(3)}], which is formed (in low yield) by reaction between cis-[(hppH)(2)PtCl(2)] and H(2)O(2) in CH(3)CN.     

1,2-Bis(2,5-diphenylphospholano)methane, a new ligand for asymmetric hydrogenation

1,2-Bis(2,5-diphenylphospholano)methane (Ph-BPM) has been prepared in good yield from 2,5-trans-diphenylphospholane-borane adduct. Rhodium and ruthenium complexes of this ligand have been prepared and their usefulness in asymmetric hydrogenation has been investigated. [Ph-BPM Rh(COD)]BF₄ showed high activity and selectivity for itaconate and dehydroamino acid hydrogenation. Ph-BPM RuCl₂(DPEN) was effective for imine hydrogenation.     

2,2-Bis(methoxy- and ethoxy-NNO-azoxy)propane-1,3-diol sulfonates

2,2-Bis(alkoxy-NNO-azoxy)propane-1,3-diols react with sulfonyl chlorides and trifluoromethanesulfonic anhydride in the presence of bases affording previously unknown methane-, trifluoromethane-, benzene and toluenesulfonates (sulfonic esters) of 2-bis(methoxy- and ethoxy-NNO-azoxy)propane-1,3-diols. The triflates are thermally less stable than mesylates, benzenesulfonates, and tosylates of the corresponding diols.     

1,2-双(四甲基环戊二烯基)四甲基二硅烷与六碳基钼的反应

1,2-双(四甲基环戊二烯基)四甲基二硅烷与正丁基锂作用生成(四甲基二硅撑)双(四甲基环戊二烯基负离子盐),后者随即与六碳基钼反应形成1,1'-(四甲基二硅撑)双(四甲基环戊二烯基铝负离子盐)-(Me₂SiSiMe₂)[Me₄CpMo(CO)₃-Li⁺]₂(I),I与冰醋酸作用,随即分别与CCl₄,NBS及I₂反应,生成相应的铝卤化合物(Me₂SiSiMe₂)[Me₄CpMo(CO)₃X]₂[X=Cl(1),Br(2),I(3)].I与CH₃I反应,在钼原子上发生烃基化,得到产物(Me₂SiSiMe₂)[Me₄CpMo(CO)₃Me]₂(4);I与单质I₂直接反应,生成脱硅桥产物Me₄Cp(CO)>₃I(5).经元素分析、IR及¹HNMR表征了化合物1-5的结构。     

Das 1,2-Bis(trimethylsilyl)3,4-di(tert-butyl)cyclotetraphosphan

1,2-Bis(trimethylsilyl)-3,4-di(tert-butyl) cyclotetraphosphane cis-P₄(SiMe₃)₂(CMe₃)₂ 1 could be prepared by the reaction of (Me₃Si)₂P—P(SiMe₃)—P(SiMe₃)CMe₃ 2 with (Me₃C)PCl₂ 3 The compound 1 forms pale yellow crystals, m. p. 116°C. The ³¹P- and ¹H-NMR data of 1 are given.     

2,6-Bis(benzoxazoyl)pyridine (bzpybox) as a new dialkylammonium cation receptor

2,6-Bis(2-benzoxazoyl)pyridine (bzpybox) ligand is reported as a new artificial receptor for secondary dialkylammonium.     

Beiträge zur Chemie der Silicium–Stickstoff-Verbindungen. CXXXI. 1,2-Bis(organy lamino)-tetramethyldisilane und ihre Überführung in N,N′-Bis(organyl)oktamethyl-tetrasiladiazacyclohexane

Chemistry of Silicon-Nitrogen Compounds. CXXXI. 1,2-Bis (organylamino) - tetramethyldisilaries and their Transformation into N,N′-Bis (organyl) octamethyltetrasiladiaza-cyclohexanes 1,2-Bis(organylamino)disilanes A 1–4 were prepared via equ. 3 by aminolysis of 1,2-dichlorotetramethyldisilane and transformed by three different methods (equ. 7; 8/9 and 10/11) into the N,N′ variied tetrasiladiazacyclohexanes B 2–5. Physical, analytical and structural information can be taken from tables 1-3. The bond increments (N)Si? Si(N) of the EISENLOHR molar refractions MR_E were reinvestigated with 24.5 instead of 30.0.     

An Efficient Preparation of 1,2-Bis(Dipyrrin-9-Ylene)-Ethane,the First Fully Conjugated b-Homobilin

1,2-Bis(dipyrrin-9-ylene)-ethane 1, the first fully conjugated b-homobilin, was synthesized in two steps with excellent yield by first condensing 1,2-bispyrrylethane 3 with 2 molecular 5-formylpyrrole 4, followed by dehydration of the result 1,2-Bis(dipyrrin-9-yl)-ethane 2 with DDQ in dichloromethane. The chemical and spectroscopic properties of this novel chromophoric system are discussed.     

9,10-双-(对-(甲氧基二缩三乙二醇基)苯基乙炔基)蒽的合成、自组装及其光谱分析

通过Sonogashira偶联等反应,合成了三嵌段化合物9,10-双-(对-(甲氧基二缩三乙二醇基)苯基乙炔基)蒽,通过¹H NMR和基质辅助激光解吸电离时间飞行质谱(MALDI-TOF-MS)对其结构进行了表征。利用差示扫描量热仪(DSC)、偏光显微镜(POM)及小角X射线散射仪(SAXS)等技术手段对其本体自组装行为进行了研究,结果表明,化合物在固态相自组装成近晶A相(SmA相)。光谱分析表明,该化合物继承了二取代蒽类发光材料具有高荧光量子产率(Φ_f)的特点,是一种性能良好的光致发光材料。     

双呋喃氟脲嘧啶的晶体结构

1,3-双(2′-四氢呋喃)-5-氟脲嘧啶(简称FD-1)晶体属三斜晶系,α=8.911(4),b=11.744(5),c=12.320(7)Å,α=99.69(4)°,β=93.49(4)°,γ=97.83(4)°。空间群为P1,Z=4。R=0.089。对比了FD-1,FT-207和5-Fu三个同系列抗癌药物结构及其抗癌疗效。     

Synthesis and Crystal Structure of cis-[1,2-Bis(phenyl-thiomethyl)benzene]dichloroplatinum(Ⅱ)·0.5acetonitrile

1 INTRODUCTION The coordination chemistry of bithioethers with noble metal ions has received considerable attention for a very long time due to their appli- cations in extracting noble metals. A number of Pt(Ⅱ) complexes with such ligands have been reported[1～7], among which some crystal structures have been determined[4～7]. However, most of these structures are Pt(Ⅱ) complexes of a few bithioether ligands with flexible alkyl spacers, RS(CH2)nSR. To our knowledge, the crystal str…     

2,6-Bis(2-benzimidazolyl)pyridine as a chemosensor for fluoride ions

2,6-Bis(2-benzimidazolyl)pyridine, a neutral tridentate ligand, is employed as a chemosensor for the detection of fluoride ions. The binding of anionic guest species with this ligand is studied using UV-vis spectroscopy, fluorescence spectroscopy, and ¹H NMR techniques. The results indicate that 2,6-bis(2-benzimidazolyl)pyridine can be used as a chemical shift and optical modification based sensor for the detection of fluoride ions.     

Reaktionen von 1,2-Bis(trimethylsilyl)iminen mit Selen-und Tellur-halogeniden

Reactions of 1,2-Bis(trimethylsilyl)imines with Selenium and Tellurium Halogenides The reactions of benzil-bis(trimethylsily)imine and phenanthrene-9,10-bis(trimethylsilyl)imine with SeOCl₂, SeCl₄ and TeCl₄ are described.     

基于2,6-二(4-羧基苯亚甲基)环己酮的金属-有机框架化合物的合成与表征

以2,6-二(4-羧基苯亚甲基)环己酮(H₂L)为配体得到一例锰金属-有机框架化合物[MnL]_n,并运用红外、热重、循环伏安、固体紫外、X射线光电子能谱和X射线单晶衍射对其进行表征。单晶衍射分析表明该配合物属于三斜晶系,空间群P1^-,不对称单元由Mn(Ⅱ)离子和一个L^2-配体组成。配体两端的羧基均为单齿配位,配体中间羰基上的氧参与配位,每个配体L^2-和3个Mn.离子配位,形成相对稳定的三角形配位构型。配合物中的Mn.与氧原子形成六配位构型,其中赤道面中的4个氧原子来自4个配体L^2-中单齿配位的羧基,上下顶点的2个氧原子分别来自配体L^2-中的羰基,从而形成八面体构型[MnO₆]。拓扑分析表明该金属-有机框架化合物具有二维kgd结构特征。循环伏安测试表明在扫速为30 mV·s^-1时,半波电位为171 mV,固体紫外光谱表明该化合物的带隙为1.76 eV。该化合物在染料分子如亚甲基蓝、甲基橙的降解过程中,具有一定的光催化活性。     

2,5-双(对二甲氨基苯乙烯基)吡嗪的双光子诱导荧光性质

本工作合成了具有D-π-A-π-D对称结构的化合物2,5-双(对二甲氨基苯乙烯基)吡嗪。利用飞秒激光器研究了2,5-双(对二甲氨基苯乙烯基)吡嗪的双光子吸收特性,获得了在820 nm处的最大双光子吸收截面(σ= 212 GM)。荧光发射强度与激发光强平方的线性关系证明了2,5-双(对二甲氨基苯乙烯基)吡嗪的双光子诱导发光机制。     

Alkoxylation of 1,2-Bis(methylchlorosilyl)ethylenes and -Acetylenes

Reactions of a series of 1,2-bis(methylchlorosilyl)ethylenes and -acetylenes Me_nCl_{3 - n}Si-Z-SiCl_{3 - n}Me_n (Z = CH = CH, CC; n = 0-2) with ethanol and acetoxime were studied. Novel alkoxy- and isopropylideneaminooxysilanes were obtained and characterized. A relation was found between the activity of Si-Cl bonds in the reactions studied and the structure of the carbon-carbon bridge.     

Synthesis of 1,4-Bis(chloromethyl) Benzene with Different Alkoxy-Substituents

l,4-Bis(chloromethyl) benzene (BCMB) and its derivatives are very important intermediates of much synthetic reaction. Especially, they can be used to synthesize poly(p-phenylene vinylene) (PPV) and its alkoxy derivatives, which have aroused significant interest in recent years^[l,2]. So people pays close attention to the synthesis of BCMB derivatives. There are several methods to synthesize BCMB derivatives, such as applying HCHO or (HCHO)n with concentrated hydrochloric acid or anhydrous HCl in the presence of zinc chloride, adopting (HCHO)n with hydrochloric acid in acetic acid aqueous, or utilizing HCHO reacts with hydrochloric acid and bubbles anhydrous HCl which was so called Wood method^[3].The methods mentioned above usually affored low yield of BCMB substituted by long alkoxy group, while the synthesis of BCMB with long alkoxy-substituents are the essential for the synthesis of soluble PPV derivatives^[4,5].     

Spectroscopic and structural studies of 6,6′-bis(N-methylhydrazine)-2,2′-bipyridine and its mononuclear copper(II) complex

The tetradentate ligand, 6,6′-bis(N-methylhydrazine)-2,2′-bipyridine (L) and its mononuclear copper(II) complex [Cu(L)](ClO₄)₂] (1) have been synthesized and characterized. The crystal structures of L and 1 have been determined by single-crystal X-ray diffraction. Both crystallize in the centrosymmetric monoclinic space group with crystallographic inversion symmetry. The ligand adopts a planar transoid configuration in the solid state. In 1, the Cu(II) is six-coordinate octahedral, defined by N₄O₂ donors from ligand and two perchlorates. The molecular units are connected by intermolecular H-bonds between the hydrazino group of the one unit and coordinated perchlorate of the neighboring two units via N–H ··· O to furnish a 2-D network. Coordinated perchlorates also form an intramolecular H-bond with hydrazine influencing the crystal packing.