聚γ-(m-二苯膦苯基)丙基硅氧烷——铂络合物对烯烃硅氢化反应的催化特征

本文报道二氧化硅负载的三苯膦铂络合物——聚γ-(m-二苯膦苯基)丙基硅氧烷铂络合物对三甲氧基硅烷与不饱和化合物进行硅氢加成反应的催化特性.在底物用量的万分之一摩尔量的铂络合物存在下,1-己烯、1-癸烯、1-十二碳烯、苯基烯丙醚和ω-氯代十一碳烯在60或40℃平稳地与三甲氧基硅烷发生硅氢加成反应,唯一地得到末端加成产物,产率均在85％以上.其催化活性在反应初期低于四(三苯膦)合铂,但后期反应速度和硅氢化产率均较高.实验表明,聚γ-(m-二苯膦苯基)丙基硅氧烷与四(三苯膦)合铂反应制得的铂络合物(1)比与氯铂酸反应制得的铂络合物(Ⅱ)催化活性高.其次,反应气氛对硅氢加成反应具有决定性的影响.在空气气氛中,硅氢化反应平稳地进行;在氮气气氛中,不发生反应.     

聚-4-氧杂-6,7-双二苯膦基庚基硅氧烷铑配合物的合成及其催化硅氢化性能

4-氧杂-6,7-二氯庚基三甲氧基硅烷依次与二苯膦钾、气相法二氧化硅、三氯化铑作用,合成了聚-4-氧杂-6,7-双二苯膦基庚基硅氧烷铑配合物。它对烯烃与取代烯烃的硅氢化反应具有良好的催化活性。     

聚ω-(甲硫基)十二烷基硅氧烷铂络合物的合成与催化性能

ω-氯代十一碳烯与甲硫醇铂在无水乙醇中反应, 得到ω-十一碳烯基甲硫醚. 后者与三甲氧基硅烷在四(三苯膦)合钼催化下进行硅氢加成, 得到ω-(甲硫基)十一烷基三甲氧基硅烷. 上述硅单体用气相法二氧化硅固载, 再与氯亚铂酸钾反应, 合成了聚ω-(甲硫基)十一烷基硅氧烷铂络合物. 其结构通过元素分析与光电子能谱进行了表征. 研究了它对烷氧基硅烷与不饱和烃的硅氢加成反应的催化特性.     

聚ω-(甲硫基)十一烷基硅氧烷铂络合物的合成与催化性能

ω-氯代十一碳烯与甲硫醇钠在无水乙醇中反应,得到ω-十一碳烯基甲硫醚。后者与三甲氧基硅烷在四(三苯膦)合钼催化下进行硅氢加成,得到ω-(甲硫基)十一烷基三甲氧基硅烷。上述硅单体用气相法二氧化硅固载,再与氯亚铂酸钾反应,合成了聚ω-(甲硫基)十一烷基硅氧烷铂络合物。其结构通过元素分析与光电子能谱进行了表征。研究了它对烧氧基硅烷与不饱和烃的硅氢加成反应的催化特性。     

二氧化硅负载苯并氮杂15—冠—5铂、铑配合物的合成及其催化硅氢化性能

N—烯丙基—2,3—苯并—1,4,7,13—四氧杂—10—氮杂环十五碳烯—2依次与三乙氧基硅烷、气相法二氧化硅、氯亚铂酸钾或三氯化铑反应,合成了相应的二氧化硅负载苯并氮杂15—冠—5铂、铑配合物,二者均为烯烃硅氢加成反应的有效催化剂。     

聚-4-氧杂-6,7-双二苯膦基庚基硅氧烷铂配合物的合成及其在烯烃硅氢化反应中的催化性能

高分子负载膦铂配合物是一类很好的烯烃硅氢加成催化剂,但迄今未见有关螯合型双膦铂配位负载催化剂的报道。1983年,Micholska报道了胺膦双齿配体铑配合物的合成与催化性能。最近,我们合成了气相法二氧化硅负载的聚-4-氧杂-6,7-双二苯膦庚基硅氧烷     

聚γ-(m-二苯胂苯基)丙基硅氧烷铂络合物的合成及其催化硅氢化性能

硅氢化反应在有机硅化学和有机硅工业中占有重要地位。早期广泛使用氯铂酸异丙醇体系作为催化剂,70年代后开始用四(三苯膦)合铂、氯化三(三苯膦)合铑等均相络合催化剂,但相应的胂络合物的催化硅氢化的研究报道极少,迄今只看到四(三苯胂)合钯、二卤化二(三苯胂)合镍、氯化二(三苯胂)(羰基)合铑等个别报道,以及三苯胂作为氯铂酸助催化剂的报道。     

二氧化硅-聚硅氧烷负载硫杂-15-冠-5铂、铑配合物的合成及其催化硅氧化性能

6－(ω'-十一碳烯氧甲基)-1-硫杂-4,7,1O,13-四氧杂环十五烷与三乙氧基硅烷进行硅氢加成,产物依次以气相法二氧化硅固载、氯亚铂酸钾或三氯化铑络合,合成了相应的二氧化硅-聚硅氧烷负载硫杂-15-冠-5-铂、铑配合物,并研究了它们在烯烃与三乙氧基硅烷的硅氢加成反应中的催化性能.结果表明,二者均为硅氢加成反应的高效催化剂.     

新型高分子负载硅氢化催化剂-聚γ-(p—二苯胂苯基)丙基硅氧烷铂络合物

三苯膦广泛用作均相络合催化剂或负载型络合催化剂的配体,但相应的三苯胂络合物研究得较少,特别是它们对硅氢加成反应的催化性能,迄令只有四(三苯胂)合钯、二卤化二(三苯胂)合镍、氯化二(三苯胂)合铑等个别报道,以及三苯胂作为氯铂酸的助催化剂的一些研究.高分子负载过渡金属三苯胂络合物,特别是它们对于烯烃硅氢加     

二氧化硅—聚硅氧烷负载硫杂—15—冠—5,铂,铑配合物的合成…

６－（ω′－十一碳烯氧甲基）－１－硫杂－４，７，１０，１３－四氧杂环十五烷与三乙氧基硅烷进行硅氢加成，产物依次以气相法二氧化硅固载，氯亚铂酸钾或三氯化铑络合，合成了相应的二氧化硅－聚硅氧烷负载硫杂－１５－冠－５－铂，铑配合物，并研究了它们在烯烃与三乙氧基硅烷的硅氢加成反应中的催化性能，结果表明，二者均为硅氢加成反应的高效催化剂。     

Nickel(II)-triphenylphosphine complexes of ONS and ONN chelating 2-hydroxyacetophenone thiosemicarbazones

The complexes [Ni(L¹)(PPh₃)] (1) and [Ni(L²)(PPh₃)]·HCl (2) were synthesized by the reaction of [Ni(PPh₃)Cl₂] and dibasic 2-hydroxyacetophenone-S-R-4-R¹-thiosemicarbazones (R/R¹: H/CH₃, L¹H₂; CH₃/H, L²H₂). The ligands and the complexes were characterized using elemental analysis, IR and ¹H NMR spectra. In both complexes, the thiosemicarbazone ligands coordinate to nickel(II) by giving two protons. Complex 1 is formed through the phenolate oxygen, azomethine nitrogen and sulfur atoms of L¹ and the P atom of a triphenylphosphine ligand. In complex 2, L² is functional through an ONN donor set, containing a thioamide nitrogen instead of a sulfur atom. X-ray analysis indicated distorted square planar structures for the complexes, and the nickel atoms lie slightly above the planes structured by the donor atoms. In the crystal forms of 1 and 2, some phenyl ring protons of the phosphine ligand give intramolecular hydrogen bonds with the donor atoms of the thiosemicarbazone moiety, namely the phenolate oxygen (in complexes 1 and 2) and N⁴ nitrogen (in complex 2).     

正丁基黄原酸铜与三苯基膦配合物的结构和表征

合成并通过IR、UV、~1HNMR、TGA及单晶X射线衍射研究了正丁基黄原酸铜与三苯基膦配合物的结构和性能。该配合物属单斜晶系,空间群P2_1/c,晶胞参数为:a=11·000(2),b=20·090(4),c=17·320(4),β=103·800(3)°,V=3717·1(13)~3,Z=4。中心铜原子与来自正丁基黄原酸根的两个硫原子及三苯基膦的两个磷原子配位,呈扭曲的四面体构型。IR,UV及~1HNMR分析结果与晶体结构一致。热重分析研究表明该配合物从110℃开始分解,到295℃分解完全,留下CuS。     

Applications of a monomeric orthopalladate complex containing mixed phosphorus-nitrogen donors in the Heck reaction

The [Pd{C₆H₂(CH₂CH₂NH₂)-(OMe)₂,3,4}Br(PPh₃)] monomeric orthopalladate complex of homoveratrylamine and triphenylphosphine was synthesized and its application in Heck coupling reactions was investigated. This complex had been demonstrated to be more active than the corresponding dimeric catalyst for Heck reactions of aryl iodides, bromides and even chlorides and also arenesulfonyl chlorides. The cross-coupled products were produced in excellent yields using catalytic amounts of [Pd{C₆H₂(CH₂CH₂NH₂)-(OMe)₂,3,4}Br(PPh₃)] as a thermally stable and oxygen insensitive complex in NMP at 130 °C.     

Electroreduction of tetra-coordinate phosphonium derivatives; one-pot transformation of triphenylphosphine oxide into triphenylphosphine

Electroreduction of triphenylphosphine dichloride in acetonitrile was performed successfully in an undivided cell fitted with an aluminium sacrificial anode and a platinum cathode, wherein Al³⁺, which was electrogenerated at the anode would react as a Lewis acid with triphenylphosphine dichloride to afford tetra-coordinate chlorotriphenylphosphonium species and subsequent two-electron reduction at the cathode would give triphenylphosphine. One-pot transformation of triphenylphosphine oxide to triphenylphosphine was achieved successfully by the treatment of triphenylphosphine oxide with oxalyl chloride and subsequent electroreduction. In a similar manner, some tetra-coordinate triphenylphosphonium species derived from triphenylphosphine oxide were reduced electrochemically to triphenylphosphine in moderate yields.     

A structural, spectroscopic and theoretical study of the triphenylphosphine chalcogenide complexes of tungsten carbonyl, [W(XPPh3)(CO)5], X=O, S, Se

The series [W(XPPh₃)(CO)₅], X=O, S, Se has been structurally determined by X-ray crystallography and fully characterised spectroscopically to provide data for comparing the bonding of the Ph₃PX ligands to the metal. The P-X-W angles are 134.3°, 113.2° and 109.2°, respectively, for X=O, S, Se. The bonding has been analysed using EHMO calculations which suggest that lower P-X-W angles depend on the relative importance of σ-bonding, which in turn depends on the chalcogen in the order X=Se > S > O. The effect is enhanced by lower energies of the metal σ and π orbital energies.     

Rh/Ph3PO催化剂体系的辛烯氢甲酰化反应性能考察和原位红外表征

考察了反应温度,ＣＯ／Ｈ２压力和Ｐ／Ｒｈ比等因素,对Ｒｈ／Ｐｈ３ＰＯ催化剂催化混合辛烷氢甲酰化反应活性的影响,优化出最佳反应条件,并采用加热加压的原位红外表征方法,跟踪了在１－辛烯反应中Ｒｈ／Ｐｈ３ＰＯ催化剂的活化、中间活性物种的产生和分解消失等瞬态变化情况。     

A RAPID AND FACILE CONVERSION OF PRIMARY AMIDES AND ALDOXIMES TO NITRILES AND KETOXIMES TO AMIDES WITH TRIPHENYLPHOSPHINE AND N-CHLOROSUCCINIMIDE

ABSTRACT

Primary amides and aldoximes are easily converted to their corresponding nitriles using a mixture of triphenylphosphine and N-chlorosuccinimide in dichloromethane at room temperature. The reaction of aldoximes occurs almost immediately and primary amides in 0.5?h by this method. By this procedure secondary amides are produced by Beckmann rearrangement of ketoximes.     

钯－膦－酸体系催化叔丁醇羰化制备异戊酸酯

研究了Ｐｄ（ＯＡｃ）２－ＰＰｈ３－ｐ－Ｔｓ催化剂体系存在下，叔丁醇羰化生成异戊酸酯的反应．典型的反应条件是：温度１２０～１６０℃，压力３．０～７．０ＭＰａ，Ｐｄ浓度３．６ｍｍｏｌ／Ｌ，ｎＰｄ∶ｎＰＰｈ３∶ｎｐ－Ｔｓ＝１∶３０∶８０，时间１２～２４ｈ．在上述反应条件下，叔丁醇羰化生成异戊酸酯的产率为１１．０％～８３．６％，选择性为１３．１％～９５．０％．     

ORGANOPHOSPHORUS COMPOUNDS,XXXIII THE REACTION OF PHOSPHITE ESTERS WITH QUINISATIN

Abstract

Trialkyl phosphites react with quinisatin (1) and its monohydrate 3 to give the corresponding phosphate derivatives 2a-c. The same compounds are obtained upon reacting 1 and/or 3 with the proper dialkyl phosphite. Structural reasonings based on IR, MS and NMR spectral data, are presented.     

Synthesis and Characterization of O,O′ Dialkyl and Alkylene Dithiophosphates of Lanthanum(III) and their Adducts with Nitrogen and Phosphorus Donor Bases

Lanthanum(III) tris(dithiophosphates), [La{S₂P(OR)₂}₃] (where R=-CH₂CH₂CH₃ or -C₆H₅) and [La{S₂PO₂G}₃] [where G=-C(CH₃)₂CH₂CH(CH₃)-, -CH₂C(CH₃)₂CH_2-, -C(CH₃)₂C(CH₃)_2- and -CH₂CH₂CH(CH₃)-] were prepared in methanolic solutions of anhydrous LaCl₃ and ammonium dithiophosphates. Addition complexes of the type [La{S₂P(OR)₂}₃·nL] and [La{S₂PO₂G}₃·nL] [where n = 1, L = N₂C₁₀H₈ or N₂C₁₂H₈ and n = 2, L = P(C₆H₅)₃] were prepared by reaction of lanthanum(III) tris(dithiophosphates) and nitrogen or phosphorus donor bases in benzene. These newly synthesized derivatives have been characterized by elemental analyses, molecular weights, IR, ¹H and ³¹P NMR spectral measurements. Coordination numbers of six and eight are suggested for lanthanum(III) in these derivatives.