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51.
Oguejiofo T. Ujam Kyle Devey William Henderson Brian K. Nicholson Michael R. Mucalo Corry Decker 《Phosphorus, sulfur, and silicon and the related elements》2013,188(11):1508-1525
Abstract The immobilization of the dinuclear platinum(II) sulfido complex [Pt2(μ-S)2 (PPh3)4] on solid supports has been investigated. Reaction with haloalkyl functionalized polymers [Merrifield's resin (chloromethylated polystyrene), chloropropyl silica, chloropropyl controlled pore glass, and bromopropyl polysiloxane] gives complexes immobilized through alkylation of one of the sulfide ligands, forming a μ-thiolate ligand acting as an anchor to the polymer support, akin to well-established reactions of [Pt2(μ-S)2(PPh3)4] with molecular alkylating agents. The model complex [Pt2(μ-S)(μ-SCH2SiMe3)(PPh3)4]PF6 was prepared as the first molecular silicon-containing derivative of [Pt2(μ-S)2(PPh3)4] and was fully characterized by NMR spectroscopy, electrospray ionization-mass spectrometry, and single-crystal X-ray diffraction. Immobilization of [Pt2(μ-S)2(PPh3)4] by phosphine exchange reactions was also achieved using commercial polystyrene-grafted triphenylphosphine or a new immobilized phosphine [derived by sequential functionalization of Merrifield's resin with a polyether amine and then Ph2PCH2OH]. 相似文献
52.
Ngoc Hoa Tran Huy Francois Mathey 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):477-481
Abstract The reaction of electron-rich alkynes such as ethoxyacetylene or propynyldiethylamine with a transient terminal phosphinidene complex such as [PhP?W(CO)5] directly yields the corresponding phosphole complexes via a formal [2 + 2 + I] cycloaddition involving two molecules of alkyne and one phosphorus center. 相似文献
53.
Boris Trofimov Nina Gusarova Lambert Brandsma 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):601-604
Abstract Generation of phosphide anions from phosphorus red or phosphine under the action of strong bases followed by their reactions with organyl halides, electrophilic alkenes and alkynes proves to be the most straightforward and well-controlled route to mono-, di- or triorganylphosphines or phosphine oxides of diverse structure. 相似文献
54.
Tian-Bao Huang Ling-Fei Liu Xiao-Ming Yu Wen-Qian Yang Xu-Hong Qian Jingling Zhang 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):307-312
Abstract Three pathways were observed in the reactions of Schiff bases of Thiohydrazides with P(NR2)3. (a) MeS-R2N exchange: MeS-C([dbnd]S)-NHN[dbnd]CHPh (1) reacted with P(NR2)3 led to new Schiff bases, R2N-C([dbnd]S)-NHN[dbnd]CH = Ph (2). (b) Cleavage of C[dbnd]S bond and the formation of P[dbnd]S bond: H2N-C([dbnd]S)-NHN[dbnd]CH = Ph (3) reacted with P(NR2)3 gave rise to the thiophosphoric amide. (Et2N)2P([dbnd]S)-NH-CH = N-N[dbnd]CH-Ph (4). (c) Formation of thiadiazole and triazole: Schiff bases 2a and H2N(MeS)C = N-N[dbnd]CH-Ph (6) reacted with P(NR2)3 respectively and produced 5-dimethylamino-2-phenyl-2,3-(2H)-1,3,4-thiadiazole (5) and 5-methylthio-2-phenyl-2,3-(2H)-1,3,4-triazole (7). 相似文献
55.
E. Benedetti E. Chiellini E. Bencini R. Santini P. Vergamini 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):35-36
Abstract Several infrared and Raman studies have been performed on compounds containing the disulfide group in the region of C-S and S-S stretching modes (1–4) in order to get a better insight of the correlations between molecular conformation and peculiar geometry parameters of the dihedral angle CS-SC. 相似文献
56.
利用量子力学第一原理研究了储氢材料膦化三氢化铝(AlH3PH3)在催化剂膦(PH3)作用下的释氢反应机理;首先在MP2/aug-cc-pVDZ水平上计算了反应物、过渡态和产物的几何构型和频率,进而利用内禀反应坐标理论确定了反应的最小能量路径,随后在CCSD(T)/aug-cc-pVDZ水平上对基于MP2优化的几何构型进行了能量校正.结果表明,AlH3PH3释氢的能垒高于Al―P键的离解能,而催化剂PH3不能降低AlH3PH3的释氢能垒.因此,需要寻找其他的催化剂以使AlH3PH3成为一种合用的储氢材料. 相似文献
57.
Jean-Cyrille Hierso Matthieu Beaupérin Samer Saleh André Job Jacques Andrieu Michel Picquet 《Comptes Rendus Chimie》2013,16(6):580-596
Conjugated alkynes are recurring building blocks in natural products and in a wide range of important compounds, such as pharmaceuticals, agrochemicals, or molecular materials. The palladium-catalysed cross-coupling reaction between the sp2-hybridized carbon atoms of aryl, heteroaryl, and vinyl halides with the sp-hybridized carbon atoms of terminal alkynes is one of the most important developments in the field of alkyne chemistry over the past 50 years. Room for improvement still exists in these important reactions of direct arylation of terminal alkynes. In this prospect, the present authors have developed several strategies aiming at improving the reactivity, the selectivity, and several aspects of processes involving the palladium-catalysed alkyne arylation and heteroarylation reactions, in relation with sustainable chemistry. Various original approaches have thus been adopted: (i) the development of catalytic systems efficient at low metal loading below 1 mol% of palladium and copper (to reduce metal contamination) from polydentate ligands chemistry, (ii) the limitation of diyne formation by undesired side-reaction, this from a better mechanistic understanding and the innovating use of copper adducts, (iii) and the development of cost-efficient catalytic reactions in ionic liquid solvents. These topics have been developed with the general outlook of a large scope in organic synthesis. In addition, the investigation of recycling opportunities and the unprecedented production of extendedly conjugated bis(aryl)diynes has been also achieved. The present account reviews all this work, as it has been presented by the corresponding author at GECOM–CONCOORD 2012 as recipient of the 2012 European journal of Inorganic Chemistry Young Investigator Award. 相似文献
58.
Saied Saeed Hosseiny Davarani Hamid Reza Moazami Ali Reza Keshtkar Mohammad Hossein Banitaba Saeed Nojavan 《Analytica chimica acta》2013
A novel method for the selective electromembrane extraction (EME) of U6+ prior to fluorometric determination has been proposed. The effect of extraction conditions including supported liquid membrane (SLM) composition, extraction time and extraction voltage were investigated. An SLM composition of 1% di-2-ethyl hexyl phosphonic acid in nitrophenyl octyl ether (NPOE) showed good selectivity, recovery and enrichment factor. The best performance was achieved at an extraction potential of 80 volts and an extraction time of 14 minutes Under the optimized conditions, a linear range from 1 to 1000 ng mL−1 and LOD of 0.1 ng mL−1 were obtained for the determination of U6+. The EME method showed good performance in sample cleanup and the reduction of the interfering effects of Mn2+, Zn2+, Cd2+, Ni2+, Fe3+, Co2+, Cu2+, Cl− and PO43− ions during fluorometric determination of uranium in real water samples. The recoveries above 54% and enrichment factors above 64.7 were obtained by the proposed method for real sample analysis. 相似文献
59.
Ivaylo K. Ivanov 《合成通讯》2013,43(6):800-809
Diphenyl 3-methyl-penta-1,2,4-trienyl phosphine oxide can be readily prepared via an atom-economical [2,3]-sigmatropic rearrangement of the mediated alkenynyl phosphinite formed in situ by reaction of 3-methylpent-1-en-4-yn-3-ol with diphenylchlorophosphine. Electrophilic cyclization reactions of the vinylallenyl phosphine oxide prepared were investigated as it was established that the reactions proceeded with formation of various heterocyclic or highly unsaturated compounds with participation of the allenic and/or 1,3-dienic part of the vinylallenic system with neighboring group participation of phosphoryl and/or vinylic group. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file. 相似文献
60.
Nina K. Gusarova Pavel A. Volkov Nina I. Ivanova Boris G. Sukhov Ludmila I. Larina Olga N. Kazheva Grigorii G. Alexandrov Oleg A. D’yachenko Boris A. Trofimov 《Tetrahedron letters》2013
The oxidative cross-coupling between 4-hydroxy-6-methyl-2-pyrone or 3-hydroxy-2-methyl-4-pyrone and secondary phosphine chalcogenides proceeds in CCl4/Et3N under mild conditions (20–52 °С, 0.75–10 h) through the hydroxyl group to give O-(6-methyl-2-oxo-2H-pyran-4-yl) diorganylphosphinochalcogenoates or O-(2-methyl-4-oxo-4H-pyran-3-yl) diorganylphosphinochalcogenoates, in high yields. 相似文献