主链含有冠醚基团的聚硅氧烷及其铂配合物的催化硅氢化性能

报道了一种合成主链含有冠醚基团的聚硅氧烷的方法.首先,从适当的冠醚出发,合成带有两个烯基侧链的双套索冠醚,再与含氢硅单体进行硅氢加成.合成两端带有烷氧硅基的含冠醚基的硅单体,然后与八甲基环四硅氧烷共聚合,得到标题聚硅氧烷.后者与氯亚铂酸钾反应,得到相应的铂配合物,该配合物对于烯烃与三乙氧基硅烷的硅氢加成反应具有催化活性.     

十一碳烯氧甲基苯并冠醚的合成与团载化及固载化产物的催化硅氢化性能

十一碳烯氧甲基一缩二乙二醇、二缩三乙二醇分别与１，２－β（β－羟乙氧基）苯双对甲苯磺酸酯在氢化钠存在下关环缩合，得到９－十一碳烯氧甲基－２，３－苯并１５－冠－５与９－十一碳烯氧甲基－２，３－苯并１８－冠－６．二者与三乙氧基硅烷反应产物以二氧化硅固载化，得到具有十一烯氧甲基连接基团的二氧化硅固载苯并冠醚．它们可与铂形成配合物．铂配合物对烯烃与三乙氧基硅烷的硅氢加成反应具有极好的催化效能     

具有中心功能基的网状聚合物冠醚Ⅱ．具有硫醚侧基的网状聚合物冠醚及其铂配合物的合成

通过β－乙硫乙基环氧丙基醚与一缩二乙二醇双环氧丙基醚开环共聚，合成了网状结构单元中具有硫醚侧基的网状聚合物冠醚，或交联大环聚醚。这类聚合物与铂金属形成的配合物，是烯烃与三乙氧基硅烷硅氢加成反应的高活性催化剂。     

二氧化硅固载硫、氮杂冠醚铂配合物的合成及其催化烯烃硅氢化性能

二(β-氯乙基)烯丙胺与3,6-二氧杂辛-1,8-二硫醇在乙醇钠存在下关环缩合,得到具有烯基侧链的1,7-二硫杂-10,13-二氧杂-4-氮杂-4-烯丙基环十五烷.后者通过硅氢加成、二氧化硅固载.再与氯亚铂酸钾反应,合成了一种新型有机硅聚合物负载硫、氮杂冠醚及其铂配合物.该配合物对于烯烃硅氢加成反应具有良好的催化性能.     

Functionalization of surface‐grafted polymethylhydrosiloxane thin films with alkyl side chains

Thin films of crosslinked polymethylhydrosiloxane (PMHS) have been grafted on silica using the sol–gel process allowing further functionalization by effective quantitative hydrosilylation of SiH groups by olefins within the network. Postfunctionalization gives the polysiloxane network with n‐alkyl side chains. The PMHS coating was prepared by room temperature polycondensation of a mixture of methyldiethoxysilane HSiMe(OEt)₂ monomer and triethoxysilane HSi(OEt)₃ (TH) as crosslinker. The surface‐attached films are chemically stable and covalently bonded to the silica surface. Subsequently, films were functionalized without delamination. We showed by FTIR spectroscopy how the crosslinking ratio and the molecular size of the alkenes precursors influence the extent of the hydrosilylation reaction of SiH groups in the PMHS network. We have determined that quasi‐full olefin addition catalyzed by a platinum complex occurred within soft networks of less than 5% TH with 1‐alkenes CH₂?CH(CH₂)_n‐2CH₃ of various alkyl chain lengths (n = 5, 11, 17). Powders of PMHS gel were also modified with 1‐alkenes by hydrosilylation. The SiH groups within the soft gel (5% crosslinked) were fully functionalized as shown by ²⁹Si and ¹H solid‐state NMR. The structure of functionalized polysiloxane with n‐octadecyl and n‐dodecyl side chains was studied by FTIR, wide angle X‐ray diffraction, and DSC showing crystallization of the long n‐alkyl chains in the network. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3546–3562, 2008     

CROWN FUNCTIONALIZED LINEAR POLYSILOXANE PLATINUM COMPLEX AS HYDROSILYLATION CATALYST

A modified method of preparing crown functionalized linear polysiloxane has been described.4'-allylbenzo-15-crown-5 was subjected to hydrosilylation with methyldichlorosilane,followed bypolycondensation with silanol-terminated polydimethylsiloxane to give the title crownfunctionalized linear polysiloxane. It was found that the polysiloxane could be coordinated withplatinum salt to form platinum complex, which could catalyze the hydrosilylation of olefins withtriethoxysilane efficiently.     

SYNTHESIS OF POLYSILOXANE-SUPPORTED SELENAETHER PLATINUM COMPLEX AND ITS CATALYTIC PROPERTY FOR HYDROSILYLATION OF OLEFINS

A new type of selenious polymer, silica-bound polybispropoxyethyl-selenidesilsesquioxane,and its platinum complex were synthesized from bis-allyloxyethyl selenide via hydrosily-lation with triethoxysilane, followed by immobilized on fumed silica, and then reactingwith potassium chloroplatinite under nitrogen atmosphere in acetone. It was found thatthe platinum complex can catalyze the hydrosilylation of olefins with triethoxysilane effec-tively The effects of the nature of the substrate, the amount of complex used, and thereaction temperature on the catalytic activity were investigated.     

Study of Karstedt's Catalyst for Hydrosilylation of a Wide Variety of Functionalized Alkenes with Triethoxysilane and Trimethoxysilane

The hydrosilylation is one of the most important methods for the synthesis of organosilicon compounds. Karstedt's catalyst [Pt_n (H₂C =CHSiMe₂OSiMe₂CH =CH₂ )_m ] is a kind of platinum catalyst which is widely used in the hydrosilylation. In this paper, we studied the catalytic activity of Karstedt's catalyst for the hydrogenation of olefins and especially aminated alkenes with trimethoxysilane and triethoxysilane, and demonstrated the excellent performance in terms of the yield and selectivity.     

SYNTHESIS AND CATALYTIC BEHAVIOR OF POLYSILOXANESUPPORTED FULLERENE PLATINUM OR RHODIUM COMPLEXES*

Two polysiloxanes with pendant fullerene moieties and their platinum or rhodium complexes havebeen prepared from C_(60) via amination with ω-decenylamine, followed by hydrosilylation with triethoxysilaneand immobilization on fumed silica or by hydrosilylation with methyldichlorosilane and polycondensationwith polydimethylsiloxanol, and then by reacting them with potassium chloroplatinite or rhodium chloride inacetone respectively under argon atmosphere. It was found that the four noble metal complexes are effectivecatalysts for the hydrosilylation of olefins with triethoxysilane. The regioselcctivity of platinum complexesfor styrene increases remarkably by introducing C_(60) moiety. Factors influencing catalytic activity and themechanism have been investigated.     

MCM‐41‐Supported Bidentate Phosphine Rhodium Complex: An Efficient and Recyclable Heterogeneous Catalyst for the Hydrosilylation of Olefins

MCM‐41‐supported bidentate phosphine rhodium complex (MCM‐41‐2P‐RhCl₃) was conveniently synthesized from commercially available and cheapγ‐aminopropyltriethoxysilane via immobilization on MCM‐41, followed by reacting with diphenylphosphinomethanol and rhodium chloride. It was found that the title complex is a highly efficient catalyst for the hydrosilylation of olefins with triethoxysilane and can be recovered and recycled by a simple filtration of the reaction solution and used for at least 10 consecutive trials without any decreases in activity.     

有机硅聚合物负载环硫乙烷铂配合物的合成与催化性能

<正> 有机硅聚合物负载硫醚与铂的配合物可作为烯烃硅氢加成的有效催化剂,但其中部分配合物的回收再用性能不太理想,合成亦比较繁琐。考虑到环硫乙烷中硫原子的未共用电子对远比一般硫醚中硫原子的未共用电子对更加暴露,有可能与过渡金属形成更稳定的配合物,从而减少催化过程中金属的流失,我们合成了气相法二氧化硅固载的聚-4-氧杂-6,7-环硫庚基硅氧烷铂配合物,研究了该配合物对烯烃硅氢加成反应的催化性能。本文报道所得到的一些结果。     

C~6~0乙醇胺铂配合物的合成及其催化硅氢化性能

C~6~0与乙醇胺反应,然后与亚氯铂酸钾络合,制得了含配位氮原子的富勒烯铂配合物。该配合物能有效地催化烯烃与三乙氧基硅烷的硅氢化反应,并对苯乙烯有独特的催化性能,以近100%的区域选择性得到α-加成产物。还对催化机理进行了初步的探讨。     

聚硅氧烷负载硫、氮-铂双齿配合物的合成及其对烯烃硅氢化的催化作用

γ-巯丙基三甲氧基硅烷与β-氯乙基二甲胺盐酸盐在甲醇钠存在下缩合,得到4-硫杂-6-二甲胺基己基三甲氧基硅烷。后者以气相法二氧化硅固载,再与氯亚铂酸钾反应,合成了二氧化硅固载的聚-4-硫杂-6-二甲胺基己基硅氧烷-铂配合物。它是烯烃硅氢加成的有效催化剂。     

SILICA-BOUND CROWN ETHERS PLATINUM COMPLEX AS HYDROSILYLATION CATALYST

Silica-bound 15-Crown-5, 18-Crown-6 with a spacer of propyloxymethyl and their platinum complexes have been synthesized. It was found that they were efficient catalysts for the hydrosilylation of olefms with triethoxysilane in the temperature range of 60 to 130 ℃.     

Preparation and Properties of C60-Polysiloxane Hybrids

C₆₀-polysiloxane hybrids were prepared by the reaction of triethoxysilylated C₆₀ (TES-C₆₀) with methylpolysiloxane (MPS) or , -dihydroxypolydimethylsiloxane (STPDS). TES-C₆₀ was synthesized by hydrosilylation using triethoxysilane and C₆₀ in the presence of chloroplatinic acid. TES-C₆₀ was mixed with MPS and heated to provide a bulk body of C₆₀ containing polysiloxane hybrid in a Si/C₆₀ molar ratio of 1000:500. The formation of this hybrid is based on the hydrolytic polycondensation of TES-C₆₀ and MPS to fix C₆₀ into the silica matrix by a chemical bond. TES-C₆₀ and STPDS also provide an isolatable thin film of C₆₀ containing polysiloxane hybrid by an ethanol-forming condensation reaction. Because no gelation was observed when only STPDS was aged, it is thought that TES-C₆₀ serves as a cross-linking point in gel formation.     

Catalytic Hydrosilylation of Substituted Acetophenones by 1,1,3,3-Tetrametyldisiloxane with Complexes Rhodium (I) and Platinum (II)

The hydrosilylation of a range of para-substituted acetophenones XC₆H₄COCH₃ (X = H, Me, MeO, F, Cl, NO₂) with 1,1,3,3-tetramethyl disiloxane mediated by complexes of rhodium (I) and platinum (II) was investigated. The complexes of platinum (II) are less effective than complexes of rhodium (I), but display greater selectivity. Six 1-(1′-arylethoxy)-1,1,3,3-tetramethyl disiloxanes have been synthesized by hydrosilylation using several coupling catalysts.     

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。     

Synthesis and Hydrosilylation of Furan and Thiophene N-Methylenefluoroanilines in the Presence of Pd(I) Complex

A series of new N-hetarylaldimines were synthesized by the reactions of furan and thiophene aldehydes with 2-, 3-, and 4-fluoroanilines in the presence of molecular sieves. The reaction of some of the synthesized azomethines with triethoxysilane in the presence of the [Pd(allyl)Cl]₂ complex was studied. It was found that the structure of the initial aldimines has an effect on the direction of hydrosilylation. All the studied substrates are transformed into the corresponding amines. The products of N- and C-silylation were also detected in the reaction mixtures. In certain cases reduction of the furan and thiophene rings occurs. Dedicated to Prof. N. S. Zefirov as a sign of respect in connection with his birthday __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1312–1319, September, 2005.     

C60正丙胺铂,铑配合物的合成及其催化硅氢化性能

Ｃ６０与正丙胺反应,然后分别与氯亚铂酸钾或三氯化铑配合,制得出含配位氮原子的富勒烯铂,铑 配合物,它们均能有效地催化烯烃与三乙氧基硅烷硅氢加成,铂配合物还对苯乙烯有独特的催化性能,以近１００％的区域选择性得到α－加成产物,对催化机理进行了初步的探讨。     

C60乙二胺衍生物铂配合物的合成及其催化硅氢化性能

C₆₀与乙二胺反应,再与氯亚铂酸钾配位,得到了一种以C₆₀衍生物为基的Pt(Ⅱ)配合物,并研究了其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,该配合物为硅氢加成反应的高效催化剂,并对苯乙烯有独特的催化性能,以近100%的区域选择性得到α-加成产物。