排序方式: 共有111条查询结果,搜索用时 31 毫秒
21.
The reaction of the complex [{(η6-C6Me6)Ru(μ-Cl)Cl}2] 1 with sodium azide ligand gave two new dimers of the composition [{(η6-C6Me6)Ru(μ-N3)(N3)}2] 2 and [{(η6-C6Me6)Ru(μ-N3)Cl}2] 3, depending upon the reaction conditions. Complex 3 with excess of sodium azide in ethanol yielded complex 2. These complexes undergo substitution reactions with monodentate ligands to yield monomeric complexes of the type [(η6-C6Me6)Ru(X)(N3)(L)] {X = N3, Cl, L = PPh3 (4a, 9a); PMe2Ph (4b, 9b); AsPh3 (4c, 9c); X = N3, L = pyrazole (Hpz) (5a); 3-methylpyrazole (3-Hmpz) (5b) and 3,5-dimethyl-pyrazole (3,5-Hdmpz) (5c)}. Complexes 2 and 3 also react with bidentate ligands to give bridging complexes of the type [{(η6-C6Me6)Ru(N3)(X)]2(μ-L)} {X = N3, Cl, L = 1,2-bis(diphenylphosphino)methane (dppm) (6, 10); 1,2-bis(diphenylphosphino)ethane (dppe) (7, 11); 1,2-bis(diphenylphosphino)propane (dppp) (8, 12); X = Cl, L = 4,4-bipyridine (4,4′-bipy) (13)}. These complexes were characterized by FT-IR and FT-NMR spectroscopy as well as by analytical data.The molecular structures of the representative complexes [{(η6-C6Me6)Ru(μ-N3)(N3)}2] 2, [{(η6-C6Me6)Ru(μ-N3)Cl}2] 3,[(η6-C6Me6)Ru(N3)2(PPh3)] 4a and [{(η6-C6Me6)Ru(N3)2}2 (μ-dppm)] 6 were established by single crystal X-ray diffraction studies. 相似文献
22.
Riadh El Abed Jean-Pierre Genêt Angela Marinetti 《Journal of organometallic chemistry》2007,692(5):1156-1160
Palladium catalysed Heck couplings have been applied to the two-step synthesis of a stilbene derivative bearing a diphenylphosphine oxide function which represents a suitable precursor for the photochemical generation of the corresponding [7]-helicene. After reduction of the phosphine oxide, resolution of the monodentate helical phosphine has been performed by means of the ortho-metallated (R)-1-(naphthyl)ethylamine-palladium complex. A ruthenium complex of (heptahelicen-2-yl)diphenylphosphine has also been prepared and fully characterized. 相似文献
23.
Abstract La sulfonation de diphosphines de type-1,2, 1–3 et 1–4 (dppe, dppp, dppb) est ttudite. II est montré que la sulfonation est plus rapide pour les diphosphines-1,4 que pour les diphosphines-1,3 et 1,2. Les conditions permettant d'accéder à la tétrasulfonation sont précisées, ainsi que celles conduisant à un mélange riche en phosphées disulfoées. Cette étude a été étendue aux diphosphines chirales (Cyclobutanediop. BDPP, Chiraphos). The sulfonation of 1,2, -1,3 and -1,4 diphosphines (dppe, dppp, dppb) is studied. It is shown that the sulfonation is faster for 1,4-diphosphines than for -1,3 and -1,2 diphosphines. The conditions affording the tetrasulfonation are described, and also those allowing the obtention of a mixture containing large amounts of disulfonated diphosphines. This study is extended to chiral diphosphines (Cyclobutanediop, BDPP, Chiraphos). 相似文献
24.
György Keglevich Melinda Sipos György Pet?cz 《Journal of organometallic chemistry》2004,689(20):3158-3162
Double deoxygenation of a 3-phosphinoxido-1,2,3,6-tetrahydrophosphine oxide (2) led to bisphosphine 3-2 with an inverted ring P atom. The reaction of bidentate P-ligand 3-2 with dichlorodibenzonitrilo platinum(II) yielded the mixture of a novel cis chelate complex (7 = PtCl2(3-2)) and a cis bis(3-diphenylphosphino-1,2,3,6-tetrahydrophosphininyl) complex (8 = PtCl2(η1-5)2) containing two units of monodentate P-ligand 5. 相似文献
25.
The title compounds react with unidentate ligands, L, containing either phosphorus or arsenic donor atoms to yield the corresponding compounds of the type Ru(η5---C5Me4Et)(CO)LX; with didentate phosphorus donor ligands the major species formed is the bridged complex {Ru(η5---C5Me4Et)(CO)X}2{Ph2P(CH2)nPPh 2} n = 1, X = Br; n = 2, X = Cl). In contrast, unidentate ligands containing nitrogen donor atoms such as pyridine did not react with Ru(η5---C5Me4Et)(CO)2Cl although reaction with 1,10-phenanthroline or diethylenetriamine yielded the ionic products [Ru(η5---C5Me4Et)(CO)L]+Cl− (L = phen or (NH2CH2CH2)2NH). Reaction of Ru(η5---C5Me4Et)(CO)2Br with AgOAc yielded the corresponding acetato complex Ru(η5---C5Me4Et)(CO)20Ac. Ru(η5--- C5Me4Et)(CO)2X reacts with AgY (Y = BF4 or PF6) in either acetone or dichloromethane to give the useful solvent intermediates [Ru(η5---C5Me4Et)(CO)2(solvent)]+Y−, which readily react with ligands L to yield ionic derivatives of the type [Ru(η5---C5Me4Et)(CO)2L]+Y− (where L = CO, NCMe, py, C2H4 or MeO2CCCCO2Me). 相似文献
26.
The reaction of [Cp*MCl4] (M = Nb, Ta; Cp* = C5Me5) with PH2R in toluene at room temperature gives the primary phosphine complexes [Cp*MCl4(PH2R)] [Cp* = C5Me5; M = Nb: R = But ( 1a ), Ad ( 2a ), Cy ( 3a ), Ph ( 4a ), 2, 4, 6‐Me3C6H2 (Mes) ( 5a ); M = Ta: R = But ( 1b ), Ad ( 2b ), Cy ( 3b ), Ph ( 4b ), Mes ( 5b )] in high yield. 1—5 were characterized spectroscopically (NMR, IR, MS) and by crystal structure determinations. The starting material [Cp*TaCl4] is monomeric in the solid state, as shown by crystal structure determination. 相似文献
27.
将 1-苯基二苯并膦 (PDBP)作为膦配体用于丙烯氢甲酰化反应中 ,系统研究了反应温度、压力、铑浓度、搅拌速率对产物丁醛收率的影响 .在铑浓度为 4.0× 10 - 6 、 P/ Rh比为 15 0、温度 10 0℃、反应压力 2 .0 MPa的条件下 ,丙烯转化率可达 90 % ,催化活性为 2 6 0 9g丁醛 / (g Rh· h) ,正丁醛和异丁醛的比达 9.5 .在相同的条件下与工业上广泛采用的以三苯基膦为配体的铑催化剂相比较 ,以 PDBP为配体的铑催化剂的活性和选择性分别是它的 1.44倍和 1.90倍 .证明了 PDBP是一个很有发展前景的羰基合成的膦配体 相似文献
28.
《高分子科学杂志,A辑:纯化学与应用化学》2013,50(5-6):653-666
The end groups of polymers prepared by atom transfer radical polymerization (ATRP), are well-defined and determined by the initiator used, at least one of them is a halogen end group. The halogen end groups can be transformed to other functionalities such as phosphonium salts as demonstrated in this paper. Kinetic studies with the compounds 1-phenylethyl bromide and methyl 2-bromopropionate, models for the polystyrene and polyacrylate chain ends respectively, indicated that bromine end groups were readily transformed to phosphonium end groups upon the addition of phosphines. Stability tests with the obtained phosphonium salts showed that 1-phenylethyl trialkylphosphonium bromide was stable, even at higher temperatures and in the presence of free phosphines. The stability of the propionate analogue was limited due to the presence of the ester group in the molecule. Polystyrene and poly(methyl acrylate) phosphonium salts were synthesized and the presence of the end groups was demonstrated by 1H NMR and ESI-MS or MALDI-TOFMS. 相似文献
29.
Properties of chiral dirhodium catalysts with ortho-metalated aryl phosphine ligands have been studied by a computational quantum chemical density functional theory method. The main aim in the current work was to systematically modify the ligand core of the Rh2(O2C R)2(PC)2 catalysts (PC is ortho-metalated aryl phosphine) in order to find structural and electronic trends involved with the modifications. The strongest impact on the properties of the active rhodium site was found when electron-withdrawing groups were introduced in the ligand core. The computational approach offers a possibility for a stepwise study of the properties of the catalysts and therefore a tool for further design of the most effective structures. 相似文献
30.
Xiu Wang 《Tetrahedron letters》2008,49(45):6442-6444
Triphenylphosphine in combination with methyl acrylate was found to be able to catalyze the Henry (nitroaldol) reaction of various aldehydes and α-keto esters to give the corresponding β-nitroalkanols in good to excellent yields, and a catalytic cycle involving a zwitterionic phosphine-alkene adduct was proposed for this dual-reagent organocatalysis according to the deuterium-labeling experiments with CD3NO2. 相似文献