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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 总被引:3,自引:0,他引:3
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. 相似文献
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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。 相似文献
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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 总被引:1,自引:0,他引:1
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. 相似文献
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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。 相似文献
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?ükriye GüveliBahri Ülküseven 《Polyhedron》2011,30(8):1385-1388
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). 相似文献
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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。 相似文献
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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. 相似文献
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Manabu KuroboshiTomotake Yano Shogo KamenoueHiromu Kawakubo Hideo Tanaka 《Tetrahedron》2011,67(32):5825-5831
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. 相似文献
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Massimiliano Arca Francesco A. Devillanova Alessandra Garau Francesco Isaia Vito Lippolis Gaetano Verani Francesco Demartin 《无机化学与普通化学杂志》1998,624(4):745-749
The reactions between triphenylphosphine sulfide (Ph3PS) and ICl in CCl4 and IBr in CH2Cl2 in 1 : 1 molar ratio give the solid adducts Ph3PS · ICl ( I ) and Ph3PS · IBr ( II ) whose structures have been solved by X-ray diffraction. Compounds I and II consist of discrete molecule units and feature the S–I–Cl or S–I–Br linear group. The S–I bond distances in I , II (2.641(1), 2.665(1) Å respectively) and in compound 2 Ph3PS · 3 I2 ( III ) (2.729(2) Å) are correlable to the net increase in the I–X (X = Cl, Br, I) bond distance. The structural features of I , II and III are in accordance with 31P CP–MAS NMR, FT-Raman and FT-IR spectral data, and elucidate the nature of the donor (Ph3PS)-acceptor (ICl, IBr, I2) interaction. 相似文献
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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. 相似文献
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《合成通讯》2013,43(16):2535-2541
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. 相似文献
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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 总被引:9,自引:2,他引:7
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。 相似文献
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M. M. Sidky M. R. Mahran A. A. El-kateb I. T. Hennawy 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3):409-412
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. 相似文献