POSSphites—monophosphites derived from incompletely condensed silsesquioxanes

A straightforward three-step synthetic route is followed to obtain nanostructured silsesquioxane based monophosphite compounds 1-3, which we named POSSphites. These compounds, derived from (c-C₅H₉)₇Si₇O₉(OH)₃ and commercially available phenol derivatives, differ mainly in the steric bulk around the phosphorus atom. Preliminary results in the rhodium-catalyzed hydroformylation of 1-octene exemplify the use of these ligands for homogeneous catalysis. High activities, with a turnover frequency of up to 5000 h⁻¹ were obtained. Ligands 1-3 are the first silsesquioxane derived monophosphite ligands to be successfully applied in homogeneous catalysis.     

VOHPO3·1.5H2O合成及表征

ＶＯＨＰＯ３·１５Ｈ２Ｏ的合成及表征王晓晗黄仲涛（华南理工大学化学工程系，广州５１０６４１）关键词亚磷酸氧钒，表征，结晶，溶剂分类号Ｏ６４３／ＴＱ１１钒磷氧化物（ＶＰＯ）是正丁烷氧化制顺酐的工业催化剂［１］，但其前驱物ＶＯＨＰＯ４·０５Ｈ２Ｏ...     

Synthesis of Diphenyl α-（Dipropoxyphosphoramido）alkyl-phosphonates

A convenient method has been developed for the synthesis of diphenyl α-（dipropoxyphosphoramido）alkyl- phosphonates under mild conditions, namely the reaction of dipropyl phosphoramidate （1） with a para（un）substituted benzaldehyde or cyclicketone （2） and triphenyl phosphite （3） by a one-pot procedure with the aid of acetyl chloride.     

Pyridine catalyzed decomposition of triphenylphosphite ozonide

Pyridine accelerates the decomposition of triphenylphosphite ozonide in CH₂Cl₂. The addition of ethanol to the (PhO)₃PO₃-C₅H₅N-CH₂Cl₂ system increases the rate of the process. The kinetic regularities of the decomposition of (PhO)₃PO₃ in the presence of pyridine, ethanol-pyridine, and propan-2-ol-pyridine mixtures in CH₂Cl₂ are studied.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 871–873, May, 1995.This work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-5231).     

含有十二元环交叉孔道的新颖亚磷酸铟[In4(HPO3)7(H2O)3](NH3CH2CH2NH3)·(H2O)的水热合成与表征

在含有HF的体系中, 用乙二胺作模板剂, 通过水热方法合成了一个新的三维亚磷酸铟[In4(HPO3)7(H2O)3](NH3CH2CH2NH3)·(H2O), 并对其进行了红外光谱、热重、ICP和CHN元素分析等表征. 单晶X射线衍射分析结果表明, 该化合物属于三方晶系, P3空间群, 晶胞参数a=1.37883(7) nm, c=0.93450(9) nm, V=1.53862(2) nm3, Z=2, Dc=2.489 Mg/m3, 最终一致性因子R1[I >2σ(I)]=0.0526, wR2[I>2σ(I)]=0.1328, GOF=1.082. 其结构中的InO6八面体、InO5(H2O)八面体和HPO3假四面体通过O原子共顶点连接, 分别沿a, b轴方向形成含有十二元环的交叉孔道, 客体水分子和双质子化的乙二胺分子存在于孔道中.     

三甲基硅取代PPO和三苯基硅取代PPO及其气体选择透过性能

讨论了聚２，６－二甲基－１，４－苯撑氧（ＰＰＯ）与三甲基氯硅烷和三苯基氯硅烷的反应，合成了一系列取代含量不同的三甲基硅取代ＰＰＯ（ＴＭＳ－ＰＰＯ）和三苯基硅取代ＰＰＯ（ＴＰＳ－ＰＰＯ）．研究了取代基团不同和取代含量变化对聚合物的气体选择透过性能的影响，发现ＴＭＳ－ＰＰＯ的气体透过系数随三甲基硅取代量加大而增高，分离系数下降；ＴＰＳ－ＰＰＯ的气体透过系数和分离系数都随三苯基硅取代量的增加而下降，ＴＰＳ－ＰＰＯ与ＴＭＳ－ＰＰＯ的气体溶解系数相近，扩散系数差别较大．故二者气体透过系数的不同主要是由于扩散系数的差异．从化学结构与气体透过性能关系的角度来看，若在聚合物分子中引入有较小转动自由能的大基团，则有利于气体分子的扩散透过．     

Interactions of carborane-containing electrophiles with triethyl phosphite. Synthesis of new carborane-containing phosphonates

The reactions ofo-carboran-l-ylethyl mesylates with triethyl phosphite and sodium diethyl phosphite were studied. Carborane-containing phosphonates were synthesized. The reaction ofo-carboranylacetyl chloride with triethyl phosphite affordedO,O-diethyl (E)-2-(o-carboran-l-yl)-1-(o-carboran-1-ylacetoxy) vinylphosphonate rather than oxo phosphonate. Dedicated to the memory of Academician M. I. Kabachnik on his 90th birthday. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2041–2044, October, 1998.     

Phosphane/phosphite silver(I) carboxylates as CVD precursors

The preparation of [L_mAgO₂CR] (L = PⁿBu₃, P(OMe)₃, P(OEt)₃; m = 1, 2; R = singly-bound organic group) and [L_mAg–E–AgL_m] (L = PⁿBu₃; E = oxalate; m = 1, 2, 3) is described. Their use as spin-on and CVD precursors is reported. SEM and EDX studies show that closed and homogeneous silver films with admirable conductivity could be obtained.     

Synthesis and Characterization of a Two‐Dimensional Zinc Phosphite,Zn3(tren)(HPO3)3·xH2O (x ≈ 0.5; tren = tris(2‐aminoethyl)amine)

A new zinc phosphite with the formula Zn₃(tren)(HPO₃)₃·xH₂O (x≈0.5) has been synthesized under hydrothermal conditions and characterized by FTIR, elemental analysis, powder X‐ray diffraction, single‐crystal X‐ray diffraction, thermogravimetric analysis and its fluorescent spectrum. The compound crystallizes in the triclinic system, space group (No.2), a = 10.1188(9) Å, b = 10.4194(9) Å, c = 10.5176(9) Å, α = 60.763(2)°, β = 70.6150(10)°, γ = 80.725(2)°, V = 912.77(14) ų, Z = 2. The structure consists of double crankshaft chains, which are linked by Zn‐O‐P bonds to form 8‐ and 12‐membered channels along the [100] direction. The claw‐like Zn‐centered complexes of Zn(N₄C₆H₁₈) as the supported templates, hang into the 12‐MR channels through Zn‐O‐P linkages with framework.     

Chirale tripod-rhodium-komplexe: Ligandsynthese, komplexchemie, katalyse

The reaction of epichlrohydrine (fx45-1) with lithium-diphenylphosphide (LiP(Ph)₂ yields the alcohol (HOCH(CH₂P(Ph)₂)₂) 1 in a stereochemically controlled reaction. To prove the constitution and coordination ability of 1, the compound has been used to synthesise the homoleptic bisdiphosphine-rhodium complexes trans/cis-[(1)₂Rh¹]B(Ph)₄2a, b. The X-ray structure of 2b shows a significant tetrahedral distortion of the planar coordination geometry theoretically favoured for a tetracoordinate metal d⁸ coordination compound. The diphosphino alcohol 1 easily reacts with chiral phosphorchloridites X₂PCI(X₂ = 2 R, 4R-2,4-pentanedioxy-3a); (±)- and R-2,2′-bi-1-naphthoxy-(3b)) to yield chiral-racemic as well as enantiomerically pure mixed donor group tripodal ligands (X₂POCH(CH₂P(Ph)₂)₂) 5a, b containing both phosphite and phosphine donor groups. The identity of these compounds has been proven by ¹H-, ³¹P- and ¹³C-NMR spectroscopy, mass-spectra and microanalysis. The coordination capabilities of these novel tripod ligands are demonstrated by the synthesis and characterisation of the chiral rhodium-cyclooctadiene complexes {[(5a,b)Rh¹(COD)]PF₆} 6a,b, which show the typical hetero-bicyclooctane tripod metal cage of this type of tripod metal template. The rhodium complexes 6a,b are catalysts for the hydrogenation of prochiral olefines. Their activity is not too high and the enantioselectivity is low. The trihapto-coordination of the tripodal ligands is more of an impediment for this type of catalytic transformation.