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1.
A new range of polar imidazolium and phosphate-containing ligands was synthesised from readily available starting materials in high yielding multi-step transformations. These ligands were used to generate Pd catalysts for Suzuki and Heck C–C coupling reactions in organic and organic/aqueous media. The catalysts performed well in aqueous media in the Suzuki reaction and less well in the Heck reaction, related to substrate solubility in the aqueous media. When moving to ionic liquids, the Heck reaction dramatically improved, especially in media compatible with the polar catalysts and the non-polar reagents. In all cases, the catalysts were stable to the formation of Pd black, a form of degradation that frequently befalls Pd catalysts. The catalysts could be successfully recycled without loss of activity. 相似文献
2.
A simple, efficient one-step route to polystyrene-supported trialkylphosphine ligands is reported. These polymer-supported alkyl phosphine ligands proved to be highly active for Suzuki-Miyaura reactions and in alkoxycarbonylation reactions. The palladium loaded polymer-supported catalysts can be recycled several times with only minimal loss of catalyst activity. 相似文献
3.
Three different syntheses of the phosphine oxazoline systems 1 are presented. Two of these approaches are divergent routes designed to involve an advanced intermediate that can be transformed into several different end-products. The third is a shorter route specifically designed to facilitate preparations of these systems on a larger scale using minimal functional group protection. Overall, eight different phosphine oxazolines were prepared. These were screened in several palladium-mediated allylation reactions. They proved to be most useful for asymmetric alkylation of 3-acetoxy-1,3-diphenylpropene and less suitable/effective for the more challenging substrates (a pentenyl derivative and a cyclohexenyl system). X-ray crystallographic analysis of the complex [(eta 3-PhCHCHCHPh)Pd(1a)][PF6] led to the conclusion that the origins of asymmetric induction in these systems might be indirectly attributed to interaction of the oxazoline-phenyl substituent with the palladium and with an allyl-phenyl substituent. Finally, data is presented for allylation of a silylenolate of an N-acyl oxazolidinone; excellent enantioselectivities and yields were obtained. 相似文献
4.
Reactions of neutral amino phosphine compounds HL1-3 with rare earth metal tris(alkyl)s, Ln(CH2SiMe3)3(THF)2, afforded a new family of organolanthanide complexes, the molecular structures of which are strongly dependent on the ligand framework. Alkane elimination reactions between 2-(CH3NH)-C6H4P(Ph)2 (HL1) and Lu(CH2SiMe3)3(THF)2 at room temperature for 3 h generated mono(alkyl) complex (L1)2Lu(CH2SiMe3)(THF) (1). Similarly, treatment of 2-(C6H5CH2NH)-C6H4P(Ph)2 (HL2) with Lu(CH2SiMe3)3(THF)2 afforded (L2)2Lu(CH2SiMe3)(THF) (2), selectively, which gradually deproportionated to a homoleptic complex (L2)3Lu (3) at room temperature within a week. Strikingly, under the same condition, 2-(2,6-Me2C6H3NH)-C6H4P(Ph)2 (HL3) swiftly reacted with Ln(CH2SiMe3)3(THF)2 at room temperature for 3 h to yield the corresponding lanthanide bis(alkyl) complexes L3Ln(CH2SiMe3)2(THF)n (4a: Ln = Y, n = 2; 4b: Ln = Sc, n = 1; 4c: Ln = Lu, n = 1; 4d: Ln = Yb, n = 1; 4e: Ln = Tm, n = 1) in high yields. All complexes have been well defined and the molecular structures of complexes 1, 2, 3 and 4b-e were confirmed by X-ray diffraction analysis. The scandium bis(alkyl) complex activated by AlEt3 and [Ph3C][B(C6F5)4], was able to catalyze the polymerization of ethylene to afford linear polyethylene. 相似文献
5.
Complexes of the type [Co(CO)n(P)5?n]ClO4, [CoH2(P)4]ClO4, [CoH(P)5](ClO4)2 and [CoHX(F)4]ClO4 (P = secondary or tertiary phosphine) have been prepared from Co(ClO4)2·6 H2O and phosphine in isopropyl alcohol. 相似文献
6.
Palladium complexes of two new types of unsymmetrical pyridyl-supported pyrazolyl-N-heterocyclic carbene ligands were synthesized and structurally characterized. A strategy to release the steric strain of the ligand was realized by the introduction of methylene linkers to the ligand molecule. All the palladium complexes exhibited good to excellent catalytic activity in Suzuki-Miyaura reactions of phenyl or p-tolylboronic acid with aryl halides including iodobenzene, aryl bromides, and activated aryl chlorides under mild conditions, revealing that the new ligands are promising for the construction of highly active transition-metal catalysts. 相似文献
7.
Alberto Scrivanti Valentina Beghetto Simonetta Antonaroli Bruno Crociani 《Tetrahedron》2005,61(41):9752-9758
The catalytic activity of η2-(olefin)palladium(0)(iminophosphine) complexes in the Suzuki-Miyaura coupling is strongly dependent on the reaction conditions and on the nature of the ligands. The reaction is at the best carried out in aromatic solvents in the presence of K2CO3 at 90-110 °C. Higher reaction rates are obtained when the R substituent on the N-imino group is an aromatic group of low steric hindrance and the olefin is a moderate π-accepting ligand such as dimethyl fumarate. At temperatures lower than 90 °C, a self-catalyzed process leading to catalyst deactivation becomes predominant. Preliminary mechanistic investigations indicate that the oxidative addition of the aryl bromide to a Pd(0) species is the rate determining step in the catalytic cycle and that the olefin plays a key role in catalyst stabilization. Systems in situ prepared by mixing Pd(OAc)2 or Pd(dba)2 with 1 equiv of iminophosphine appear substantially less active than the preformed catalysts. 相似文献
8.
A direct synthesis of conformationally mobile P,O- and P,N-type heterocyclic phosphine ligands is described involving radical-mediated addition of diisobutylphosphine to olefinic-heterocycles. Palladium complexes of the P,N-ligand were determined to be highly active in the Suzuki-Miyaura cross-coupling reactions, including deactivated aryl chlorides. 相似文献
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10.
A water-accelerated multicomponent synthesis of organic target molecules has been used as a key method for the preparation of novel barbiturate derivatives. The three-component condensation reactions of primary amines with alkyl propiolates in the presence of alloxan derivatives in water are developed as efficient and clean green synthetic procedures for the high-yielding preparation of alkyl 2-(5-hydroxy-2,4,6-trioxohexahydro-5-pyrimidinyl)-3-(alkyl or arylamino)-2-propenoates. The above synthetic protocol provides rapid access to novel and diversely substituted barbiturate derivatives. 相似文献
11.
《Journal of molecular catalysis. A, Chemical》2007,261(1):79-87
Dioxomolybdenum(VI) complexes of general formula [MoO2X2L2] (X = Cl, OSiPh3; L2 = 2-(1-butyl-3-pyrazolyl)pyridine, ethyl[3-(2-pyridyl)-1-pyrazolyl]acetate) were prepared and characterised by 1H NMR, IR and Raman spectroscopy. The assignment of the vibrational spectra was supported by ab initio calculations. A single crystal X-ray diffraction study of the complex [MoO2Cl2{ethyl[3-(2-pyridyl)-1-pyrazolyl]acetate}] showed that the compound is monomeric and crystallises in the tetragonal system with space group P41. The four complexes are active and selective catalysts for the liquid-phase epoxidation of olefins by tert-butylhydroperoxide. Selectivities to the corresponding epoxides were mostly 100% (for conversions of at least 34%) for the substrates cyclooctene, cyclododecene, 1-octene, trans-2-octene and (R)-(+)-limonene. For styrene epoxidation, the corresponding diol was also formed in significant quantities. The turnover frequencies for cyclooctene epoxidation at 55 °C were around 340 mol molMo−1 h−1 for the chloro complexes and 160 mol molMo−1 h−1 for the triphenylsiloxy complexes. The addition of co-solvents (1,2-dichloroethane or n-hexane) had a detrimental effect on catalytic activities. Kinetic studies for the two complexes bearing the ligand ethyl[3-(2-pyridyl)-1-pyrazolyl]acetate revealed an apparent first order dependence of the initial rate of cyclooctene conversion with respect to cyclooctene or oxidant concentration. 相似文献
12.
E. A. Chernyshev Z. V. Belyakova V. D. Sheludyakov V. M. Shevchenko 《Russian Chemical Bulletin》1997,46(5):1003-1006
Bis(dialkylamino)carbenium salts {[(Me2N)2CCl]+}2MCl4
2− (M=Ni, Pd) and {[Me2NC(X)NR2]+}2PtCl6
2− (R=Me, All; X=H, Cl, Me) are efficient catalysts for hydrosilylation of allyl phenyl ether, triallylamine, allyl chloride,
allylamine, and 1-octene with various hydrosilanes. The catalytic activity is dependent on the salt composition and the nature
of the metal M, the saturated compound, and the hydrosilane used. The catalysts used are usually insoluble in the reaction
mixture, active, and stable. In some cases, carbenium salts are more selective than Speier's catalyst. Novel catalysts, silica-immobilized
dialkylaminocarbenium salts, have been prepared. The kinetics of the reaction have been considered.
Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1041–1044, May, 1997. 相似文献
13.
14.
Douglas F. Foster Barry S. Nicholls Anthony K. Smith 《Journal of organometallic chemistry》1982,236(3):395-402
Reactions of Rh6(CO)16 with bis(diphenylphosphino)methane (dppm) gave Rh6(CO)14(dppm), Rh6(CO)12(dppm)2, or Rh6(CO)10(dppm)3, depending upon the reaction conditions. Rh4(CO)10(dppm) may be obtained from the reaction of Rh4(CO)12 with dppm, but this derivative rapidly decomposes in solution to give Rh4(CO)8(dppm)2, Rh6(CO)14(dppm), and Rh6(CO)12(dppm)2. Ir4(CO)10(dppm) and Ir4(CO)8(dppm)2 have also been prepared, and their structures are discussed on the basis of infrared and 31P NMR spectroscopic data. 相似文献
15.
The symmetric rhenium(V) oxo Schiff base complexes trans-[ReO(OH2)(acac2en)]Cl and trans-[ReOCl(acac2pn)], where acac2en and acac2pn are the tetradentate Schiff base ligands N,N'-ethylenebis(acetylacetone) diimine and N,N'-propylenebis(acetylacetone) diimine, respectively, were reacted with monodentate phosphine ligands to yield one of two unique cationic phosphine complexes depending on the ligand backbone length (en vs pn) and the identity of the phosphine ligand. Reduction of the Re(V) oxo core to Re(III) resulted on reaction of trans-[ReO(OH2)(acac2en)]Cl with triphenylphosphine or diethylphenylphosphine to yield a single reduced, disubstituted product of the general type trans-[Re(III)(PR3)2(acac2en)]+. Rather unexpectedly, a similar reaction with the stronger reducing agent triethylphosphine yielded the intramolecularly rearranged, asymmetric cis-[Re(V)O(PEt3)(acac2en)]+ complex. Reactions of trans-[Re(V)O(acac2pn)Cl] with the same phosphine ligands yielded only the rearranged asymmetric cis-[Re(V)O(PR3)(acac2pn)]+ complexes in quantitative yield. The compounds were characterized using standard spectroscopic methods, elemental analyses, cyclic voltammetry, and single-crystal X-ray diffraction. The crystallographic data for the structures reported are as follows: trans-[Re(III)(PPh3)2(acac2en)]PF6 (H48C48N2O2P2Re.PF6), 1, triclinic (P), a = 18.8261(12) A, b = 16.2517(10) A, c = 15.4556(10) A, alpha = 95.522(1) degrees , beta = 97.130(1) degrees , gamma = 91.350(1) degrees , V = 4667.4(5) A(3), Z = 4; trans-[Re(III)(PEt2Ph)2(acac2en)]PF6 (H48C32N2O2P2Re.PF6), 2, orthorhombic (Pccn), a = 10.4753(6) A, b =18.4315(10) A, c = 18.9245(11) A, V = 3653.9(4) A3, Z = 4; cis-[Re(V)O(PEt3)(acac2en)]PF6 (H33C18N2O3PRe.1.25PF6, 3, monoclinic (C2/c), a = 39.8194(15) A, b = 13.6187(5) A, c = 20.1777(8) A, beta = 107.7730(10) degrees , V = 10419.9(7) A3, Z = 16; cis-[Re(V)O(PPh3)(acac2pn)]PF6 (H35C31N2O3PRe.PF6), 4, triclinic (P), a = 10.3094(10) A, b =12.1196(12) A, c = 14.8146(15) A, alpha = 105.939(2) degrees , beta = 105.383(2) degrees , gamma = 93.525(2) degrees , V = 1698.0(3) A3, Z = 2; cis-[Re(V)O(PEt2Ph)(acac2pn)]PF6 (H35C23N2O3PRe.PF6), 5, monoclinic (P2(1)/n), a = 18.1183(18) A, b = 11.580(1) A, c = 28.519(3) A, beta = 101.861(2) degrees , V = 5855.9(10) A(3), Z = 4. 相似文献
16.
Zhen-Yu Tang 《Tetrahedron letters》2006,47(14):2427-2430
Readily available ferrocenylmethylphosphine was found as an efficient ligand for room temperature Ni(0)-catalyzed Suzuki-Miyaura cross-couplings of aryl arenesulfonates. Ferrocenylmethylphosphine and its polymeric form were also found as useful ligands for Ni(0)-catalyzed Suzuki-Miyaura couplings of deactivated aryl chlorides. 相似文献
17.
Douglas TM Brayshaw SK Dallanegra R Kociok-Köhn G Macgregor SA Moxham GL Weller AS Wondimagegn T Vadivelu P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(3):1004-1022
[Rh(nbd)(PCyp(3))(2)][BAr(F) (4)] (1) [nbd = norbornadiene, Ar(F) = C(6)H(3)(CF(3))(2), PCyp(3) = tris(cyclopentylphosphine)] spontaneously undergoes dehydrogenation of each PCyp(3) ligand in CH(2)Cl(2) solution to form an equilibrium mixture of cis-[Rh{PCyp(2)(eta(2)-C(5)H(7))}(2)][BAr(F) (4)] (2 a) and trans-[Rh{PCyp(2)(eta(2)-C(5)H(7))}(2)][BAr(F) (4)] (2 b), which have hybrid phosphine-alkene ligands. In this reaction nbd acts as a sequential acceptor of hydrogen to eventually give norbornane. Complex 2 b is distorted in the solid-state away from square planar. DFT calculations have been used to rationalise this distortion. Addition of H(2) to 2 a/b hydrogenates the phosphine-alkene ligand and forms the bisdihydrogen/dihydride complex [Rh(PCyp(3))(2)(H)(2)(eta(2)-H(2))(2)][BAr(F) (4)] (5) which has been identified spectroscopically. Addition of the hydrogen acceptor tert-butylethene (tbe) to 5 eventually regenerates 2 a/b, passing through an intermediate which has undergone dehydrogenation of only one PCyp(3) ligand, which can be trapped by addition of MeCN to form trans-[Rh{PCyp(2)(eta(2)-C(5)H(7))}(PCyp(3))(NCMe)][BAr(F) (4)] (6). Dehydrogenation of a PCyp(3) ligand also occurs on addition of Na[BAr(F) (4)] to [RhCl(nbd)(PCyp(3))] in presence of arene (benzene, fluorobenzene) to give [Rh(eta(6)-C(6)H(5)X){PCyp(2)(eta(2)-C(5)H(7))}][BAr(F) (4)] (7: X = F, 8: X = H). The related complex [Rh(nbd){PCyp(2)(eta(2)-C(5)H(7))}][BAr(F) (4)] 9 is also reported. Rapid ( approximately 5 minutes) acceptorless dehydrogenation occurs on treatment of [RhCl(dppe)(PCyp(3))] with Na[BAr(F) (4)] to give [Rh(dppe){PCyp(2)(eta(2)-C(5)H(7))}][BAr(F) (4)] (10), which reacts with H(2) to afford the dihydride/dihydrogen complex [Rh(dppe)(PCyp(3))(H)(2)(eta(2)-H(2))][BAr(F) (4)] (11). Competition experiments using the new mixed alkyl phosphine ligand PCy(2)(Cyp) show that [RhCl(nbd){PCy(2)(Cyp)}] undergoes dehydrogenation exclusively at the cyclopentyl group to give [Rh(eta(6)-C(6)H(5)X){PCy(2)(eta(2)-C(5)H(7))}][BAr(F) (4)] (17: X = F, 18: X = H). The underlying reasons behind this preference have been probed using DFT calculations. All the complexes have been characterised by multinuclear NMR spectroscopy, and for 2 a/b, 4, 6, 7, 8, 9 and 17 also by single crystal X-ray diffraction. 相似文献
18.
19.
The complexes PtRu(5)(CO)(15)(PMe(2)Ph)(mu(6)-C) (2), PtRu(5)(CO)(14)(PMe(2)Ph)(2)(mu(6)-C) (3), PtRu(5)(CO)(15)(PMe(3))(mu(6)-C) (4), PtRu(5)(CO)(14)(PMe(3))(2)(mu(6)-C) (5), and PtRu(5)(CO)(15)(Me(2)S)(mu(6)-C) (6) were obtained from the reactions of PtRu(5)(CO)(16)(mu(6)-C) (1) with the appropriate ligand. As determined by NMR spectroscopy, all the new complexes exist in solution as a mixture of isomers. Compounds 2, 3, and 6 were characterized crystallographically. In all three compounds, the six metal atoms are arranged in an octahedral geometry, with a carbido carbon atom in the center. The PMe(2)Ph and Me(2)S ligands are coordinated to the Pt atom in 2 and 6, respectively. In 3, the two PMe(2)Ph ligands are coordinated to Ru atoms. In solution, all the new compounds undergo dynamical intramolecular isomerization by shifting the PMe(2)Ph or Me(2)S ligand back and forth between the Pt and Ru atoms. For compound 2, DeltaH++ = 15.1(3) kcal/mol, DeltaS++ = -7.7(9) cal/(mol.K), and DeltaG(298) = 17.4(6) kcal/mol for the transformation of the major isomer to the minor isomer; for compound 4, DeltaH++ = 14.0(1) kcal/mol, DeltaS++ = -10.7(4) cal/(mol.K), and DeltaG(298) = 17.2(2) kcal/mol for the transformation of the major isomer to the minor isomer; for compound 6, DeltaH++ = 18(1) kcal/mol, DeltaS++ = 21(5) cal/(mol.K) and DeltaG(298) = 12(2) kcal/mol. The shifts of the Me(2)S ligand in 6 are significantly more facile than the shifts for the phosphine ligand in compounds 2-5. This is attributed to a more stable ligand-bridged intermediate for the isomerizations of 6 than that for compounds 2-5. The intermediate for the isomerization of 6 involves a bridging Me(2)S ligand that can use two lone pairs of electrons for coordination to the metal atoms, whereas a tertiary phosphine ligand can use only one lone pair of electrons for bridging coordination. 相似文献
20.
《Polyhedron》1987,6(6):1329-1335
The preparation and properties of cationic rhodium and iridium complexes of types [M(diolefin)L2](ClO4) and [M(diolefin)L(PPh3)](ClO4) [M = Rh, diolefin = 1,5-cyclooctadiene (COD) or 2,5-norbornadiene; M = Ir, diolefin = COD; L = phosphine sulphide] are described. The complexes have been characterized by IR, 1H NMR and 31P NMR spectroscopy. The use of [M(diolefin)L2](ClO4) as catalyst precursors in homogeneous hydrogenation of olefins has been studied. 相似文献