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Phosphine Ligands (phosphine + ligand)
Kinds of Phosphine Ligands Selected AbstractsChemInform Abstract: A New Hybrid Phosphine Ligand for Palladium-Catalyzed Amination of Aryl Halides.CHEMINFORM, Issue 32 2008Ken Suzuki Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Selective Catch and Release of a Synthetically Useful Phosphine Ligand.CHEMINFORM, Issue 1 2004Jennifer L. Marugg Abstract For Abstract see ChemInform Abstract in Full Text. [source] A Novel Chiral Ferrocenyl Phosphine Ligand from Sugar: Applications in Rh-Catalyzed Asymmetric Hydrogenation Reactions.CHEMINFORM, Issue 17 2003Duan Liu Abstract For Abstract see ChemInform Abstract in Full Text. [source] Evaluation of Electron-Deficient Phosphine Ligands for Direct Arylation of HeterocyclesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 13 2010Olivier René Abstract New electron-deficient biarylphosphine ligands were studied and proved to be efficient for the direct arylation of heteroarenes with aryl iodides. The ability of a more electron-deficient palladium centre to accelerate the arylation of heterocycles that remained unreactive with aryl iodides in the past has been validated and these heteroarenes can now be smoothly reacted in the presence of a new electrophilic catalyst. Experimental evidence suggests a viable concerted metalation,deprotonation pathway for the CH bond cleavage step with an electron-deficient palladium centre. [source] ChemInform Abstract: Modification of Chiral Monodentate Phosphine Ligands (MOP) for Palladium-Catalyzed Asymmetric Hydrosilylation of Cyclic 1,3-Dienes.CHEMINFORM, Issue 27 2001Tamio Hayashi Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Phosphine Ligands in the Palladium-Catalysed Methoxycarbonylation of Ethene: Insights into the Catalytic Cycle through an HP,NMR Spectroscopic StudyCHEMISTRY - A EUROPEAN JOURNAL, Issue 23 2010Verónica de, la Fuente Dipl.-Chem. Abstract Novel cis -1,2-bis(di- tert -butyl-phosphinomethyl) carbocyclic ligands 6,9 have been prepared and the corresponding palladium complexes [Pd(O3SCH3)(L-L)][O3SCH3] (L- L=diphosphine) 32,35 synthesised and characterised by NMR spectroscopy and X-ray diffraction. These diphosphine ligands give very active catalysts for the palladium-catalysed methoxycarbonylation of ethene. The activity varies with the size of the carbocyclic backbone, ligands 7 and 9, containing four- and six-membered ring backbones giving more active systems. The acid used as co-catalyst has a strong influence on the activity, with excess trifluoroacetic acid affording the highest conversion, whereas excess methyl sulfonic acid inhibits the catalytic system. An in operando NMR spectroscopic mechanistic study has established the catalytic cycle and resting state of the catalyst under operating reaction conditions. Although the catalysis follows the hydride pathway, the resting state is shown to be the hydride precursor complex [Pd(O3SCH3)(L- L)][O3SCH3], which demonstrates that an isolable/detectable hydride complex is not a prerequisite for this mechanism. [source] Synthesis and Reactivity of Rare Earth Metal Alkyl Complexes Stabilized by Anilido Phosphinimine and Amino Phosphine LigandsCHEMISTRY - A EUROPEAN JOURNAL, Issue 3 2007Bo Liu Abstract Anilido phosphinimino ancillary ligand H2L1 reacted with one equivalent of rare earth metal trialkyl [Ln{CH2Si(CH3)3}3(thf)2] (Ln=Y, Lu) to afford rare earth metal monoalkyl complexes [L1LnCH2Si(CH3)3(THF)] (1,a: Ln=Y; 1,b: Ln=Lu). In this process, deprotonation of H2L1 by one metal alkyl species was followed by intramolecular CH activation of the phenyl group of the phosphine moiety to generate dianionic species L1 with release of two equivalnts of tetramethylsilane. Ligand L1 coordinates to Ln3+ ions in a rare C,N,N tridentate mode. Complex l,a reacted readily with two equivalents of 2,6-diisopropylaniline to give the corresponding bis-amido complex [(HL1)LnY(NHC6H3iPr2 -2,6)2] (2) selectively, that is, the CH activation of the phenyl group is reversible. When 1,a was exposed to moisture, the hydrolyzed dimeric complex [{(HL1)Y(OH)}2](OH)2 (3) was isolated. Treatment of [Ln{CH2Si(CH3)3}3(thf)2] with amino phosphine ligands HL2-R gave stable rare earth metal bis-alkyl complexes [(L2-R)Ln{CH2Si(CH3)3}2(thf)] (4,a: Ln=Y, R=Me; 4,b: Ln=Lu, R=Me; 4,c: Ln=Y, R=iPr; 4,d: Ln=Y, R=iPr) in high yields. No proton abstraction from the ligand was observed. Amination of 4,a and 4,c with 2,6-diisopropylaniline afforded the bis-amido counterparts [(L2-R)Y(NHC6H3iPr2 -2,6)2(thf)] (5,a: R=Me; 5,b: R=iPr). Complexes 1,a,b and 4,a,d initiated the ring-opening polymerization of d,l -lactide with high activity to give atactic polylactides. [source] Chemoselective Palladium-Catalyzed Reaction in Aqueous Media: Selectivity in the Reaction of Haloanilines with 1,1-Dimethylallyl AlcoholADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 4-5 2007Yuusaku Yokoyama Abstract Palladium-catalyzed reactions of various haloanilines with 1,1-dimethylallyl alcohol were carried out in the presence of a hydrophilic ligand, 3,3,,3,,-phosphinidyne tris(benzenesulfonic acid) trisodium salt (TPPTS), or a lipophilic phosphine ligand, 1,1,-bis(diphenylphosphino)ferrocene (DPPF). The reactions proceeded chemoselectively in aqueous solvent to give C -vinylated products under basic conditions or N -allylated products under neutral conditions in practical yields (up to 79,%). The use of an aqueous solvent played an important role in this chemoselectivity and allowed the development of a one-pot synthesis of 3-methylindole. This chemoselectivity is synthetically useful because the reactive position of haloanilines can be controlled simply by changing the basicity of the reaction medium, which eliminates the need to protect the amino group during the reaction. [source] A monomeric gold(I) carbanion complex with an uncoordinated thioether: [2-(methylsulfanyl)phenyl](triphenylphosphine)gold(I)ACTA CRYSTALLOGRAPHICA SECTION C, Issue 8 2009Doris Y. Melgarejo The title compound, [Au(C7H7S)(C18H15P)], is conformationally chiral and crystallizes from benzene,hexane as individually enantiopure crystals. This mononuclear compound has the AuI atom linearly bound to a triphenylphosphine P atom and to a phenyl C atom of a 2-(methylsulfanyl)phenyl group. The angle at the AuI atom is 175.9,(2)°. The linear ligand coordination about the AuI atom has geometric parameters inside the remarkably narrow range found for gold complexes bound by a phosphine ligand and by the ortho -C atom of a substituted phenyl group. This is the first example of gold(I) attached to a methylsulfanyl aromatic carbanion. [source] Preparation of N -alkylpyridinium aryl ketone derivatives via the surfactant promoted cross-coupling reaction of N -alkylpyridiniumboronic acids with carboxylic anhydride in water at room temperatureAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 5 2009H. Matondo Abstract The palladium (II) chloride catalyzed coupling reaction of N -alkylpyridiniumboronic acids with benzoic anhydride was carried out smoothly in water to give high yields of ketones without the use of a phosphine ligand. The reaction was conducted under mild conditions at room temperature. In this article, by focusing on the Suzuki reaction, it is shown how this method can impact modern synthetic chemistry, making reactions faster, easier and cleaner. Copyright © 2009 John Wiley & Sons, Ltd. [source] Organometallic chemistry on rhodaheteroborane clusters: reactions with bidentate phosphines and organotransition metal reagents,APPLIED ORGANOMETALLIC CHEMISTRY, Issue 6-7 2003Oleg Volkov Abstract This article reviews our recent work on the reactions of the rhodaheteroboranes [8,8-(PPh3)2 - nido -8,7-RhSB9H10] (1) and [9,9-(PPh3)2 - nido -9,7,8-RhC2B8H11] (2), and their derivatives, with the bidentate phosphines, dppe [(CH2)2(PPh2)2], dppp [(CH2)3(PPh2)2], and dppm [CH2(PPh2)2], and also with organotransition metal reagents. Simple substitution of the two PPh3 ligands by a single bidentate phosphine takes place when a 1 : 1 molar ratio of base (dppe or dppp) to rhodathiaborane (1) is used. However, in the presence of an excess of dppe or dppp, products containing 1 or 2 mol of base are formed. These products include a bidentate ligand on the metal and a monodentate ligand on the cage. The displaced hydrogen atom from the cage has moved to the metal center. These bis(ligand) species are unstable with respect to the loss of dihydrogen, affording closo -11 vertex clusters with a pendent phosphine ligand on the cage. In concentrated solutions, the pendent phosphine attacks another cage to afford linked clusters. Under both sets of conditions, when dppm is used, only one product is observed. This species has two dppm ligands coordinated to the metal: one in a unidentate mode and the other bidentate. A similar product is obtained in the reaction of 2 with dppm, although the arrangement of the ligands on the metal in the product is different. Ligand exchange experiments on the dppm,thiaborane system lead to results that provide keys to the reaction pathways in some of these processes. The bis(dppm) derivatives of 1 and 2 are amenable to further derivatization. A second metal may be added, either as an exo -polyhedral atom in a nido cluster in which the metal is part of a bidentate ligand, in the case of 1 and 2, or in a closo cluster derivative of 1 in which the metal is bonded to a dangling PPh2 moiety. Thus, it was possible to add the metals iridium, rhodium or ruthenium to the cluster, in the case of 1 and ruthenium in the case of 2. However, the reaction of more electrophilic organotransition metal reagents, such as Wilkinson's catalyst, with the dppm derivative of 1 affords species resulting from removal of ligand rather than incorporation of metal, and the products shed light on the rearrangement processes in these systems. Copyright © 2003 John Wiley & Sons, Ltd. [source] A 1,2,4-diazaphospholane complex of rhodiumACTA CRYSTALLOGRAPHICA SECTION C, Issue 4 2003Robert W. Clark The crystal structure of a prospective olefin catalyst, namely {2-[1-acetyl-5-(2-hydroxyphenyl)-4-phenyl-1,2,4-diazaphospholan-3-yl]phenyl acetate-,P}chloro(,4 -cycloocta-1,5-diene)rhodium(I) dichloromethane solvate, [RhCl(C8H12)(C24H23N2O4P)]·CH2Cl2, has been determined at 173,K. The five-membered heterocycle of the phosphine ligand is in a slightly distorted twist conformation. An intramolecular N1,H1,Cl1 hydrogen bond contributes to the adopted conformation and may additionally participate in secondary interactions with substrates during catalysis. [source] Pd0 -Mediated Rapid Coupling between Methyl Iodide and Heteroarylstannanes: An Efficient and General Method for the Incorporation of a Positron-Emitting 11C Radionuclide into Heteroaromatic Frameworks,CHEMISTRY - A EUROPEAN JOURNAL, Issue 45 2009Masaaki Suzuki Prof. Abstract The Pd0 -mediated rapid trapping of methyl iodide with an excess amount of a heteroaryl-substituted tributylstannane has been investigated with the aim of incorporating a short-lived 11C-labelled methyl group into the heteroaromatic carbon frameworks of important organic compounds, such as drugs with various heteroaromatic structures, in order to execute a positron emission tomography (PET) study of vital systems. The reaction was first performed by using our previously developed CH3I/stannane/[Pd2(dba)3]/P(o -CH3C6H4)3/CuCl/K2CO3 (1:40:0.5:2:2:2) system in DMF at 60,°C for 5,min (conditions A), however, the reaction gave low yields for various heteroaromatic compounds. Increasing the amount of phosphine ligand (conditions B) led to a significant improvement in the yield, but the conditions were still not suitable for a range of basic heteroaromatic structures. Use of the CuBr/CsF system (conditions C) also provided a result similar to that obtained under conditions B with an increased amount of the phosphine. Thus, pyridine and related heteroaromatic compounds remained less reactive substrates. The problem was overcome by replacing the DMF solvent with N -methyl-2-pyrolidinone (NMP). The reaction in NMP at 60,100,°C for 5,min using a CH3I/stannane/[Pd2(dba)3]/P(o -CH3C6H4)3/CuBr/CsF (1:40:0.5:16:2:5) combination (conditions D) gave the methylated products in yields of more than 80,% (based on the reaction of CH3I) for all of the heteroaromatic compounds listed in this study. Thus, the combined use of NMP and an increased amount of phosphine is important for promoting the reaction efficiently. The use of this general approach to rapid methylation has been well demonstrated by the synthesis of the PET tracers 2- and 3-[11C]methylpyridines by using [Pd2(dba)3]/P(o -CH3C6H4)3/CuBr/CsF (1:16:2:5) in NMP at 60,°C for 5,min, which gives the desired products in HPLC analytical yields of 88 and 91,%, respectively. [source] From Solution-Phase to Solid-Phase Enyne Metathesis: Crossover in the Relative Performance of Two Commonly Used Ruthenium Pre-CatalystsCHEMISTRY - A EUROPEAN JOURNAL, Issue 17 2005Dominic E. A. Brittain Dr. Abstract A crossover in the ability of two distinct ruthenium-based metathesis pre-catalysts to effect the synthesis of dialkenylboronic esters in solution and on the solid-phase was observed. Specifically, while the Grubbs 2nd generation pre-catalyst 3 affords a greater degree of conversion to product than the Hoveyda,Grubbs pre-catalyst 2 in a solution-phase enyne-metathesis reaction, this trend is reversed in the solid-phase variant. Systematic investigation showed this trend to be general, regardless of variations in the homoallylic alcohol and alkynylboronic ester components of the reaction, as well as in the type of solid support employed. Experiments to determine a mechanistic hypothesis for this trend highlighted the significance of the ruthenium remaining bound to the substrate after metathetic rearrangement and found the presence of phosphine ligand to be detrimental to the success of the solid-phase reaction. Therefore, these results suggest an expanded role for phosphine-free pre-catalysts, such as 2, in challenging solid-phase metathesis reactions. [source] Nickel-Catalyzed Mizoroki,Heck- versus Michael-Type Addition of Organoboronic Acids to ,,,-Unsaturated Alkenes through Fine-Tuning of LigandsCHEMISTRY - AN ASIAN JOURNAL, Issue 11 2007Pao-Shun Lin Abstract Various arylboronic acids reacted with activated alkenes in the presence of [Ni(dppe)Br2], ZnCl2, and H2O in CH3CN at 80,°C to give the corresponding Mizoroki,Heck-type addition products in good to excellent yields. Furthermore, 1,equivalent of the hydrogenation product of the activated alkene was also produced. By tuning the ligands of the nickel complexes and the reaction conditions, Michael-type addition was achieved in a very selective manner. Thus, various p- and o- substituted arylboronic acids or alkenylboronic acid reacted smoothly with activated alkenes in CH3CN at 80,°C for 12,h catalyzed by Ni(acac)2, P(o -anisyl)3, and K2CO3 to give the corresponding Michael-type addition products in excellent yields. However, for m- substituted arylboronic acids, the yields of Michael-type addition products are very low. The cause of this unusual meta -substitution effect is not clear. By altering the solvent or phosphine ligand, the product yields for m- substituted arylboronic acids were greatly improved. In contrast to previous results in the literature, the present catalytic reactions required water for Mizoroki,Heck-type products and dry reaction conditions for Michael-type addition products. Possible mechanistic pathways for both addition reactions are proposed. [source] A new family of platinum(II) complexes incorporating five- and six-membered cyclic phosphine ligandsHETEROATOM CHEMISTRY, Issue 2 2010Andrea Kerényi New platinum complexes of the type cis -Pt(L)2Cl2 have been synthesized from five- and six-membered cyclic phosphines, which were prepared after deoxygenating a series of phosphine oxides (3-phospholene oxides, phospholane oxides, a 1,4-dihydrophosphinine oxide, and a 1,2,3,6-tetrahydrophosphinine oxide). The complexes were characterized by NMR and mass spectral data, and their stereostructures were elucidated by B3LYP/6-31G(d)-LANL2DZ ECP calculations. The phosphine intermediates were characterized as the corresponding phosphine-boranes. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:63,70, 2010; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20579 [source] One-Step Synthesis of Chiral Azamacrocycles via Palladium-Catalyzed Enantioselective Amination of 1,5-Dichloroanthraquinone and 1,5-DichloroanthraceneADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 13 2010Elena R. Ranyuk Abstract Asymmetric amination of 1,5-dichloroanthraquinone and 1,5-dichloroanthracene with di- and trioxadiamines catalyzed by palladium complexes with various chiral phosphine ligands gave chiral macrocycles with ee values of up to 60%. The dependence of the chemical yields and enantiomeric excess on the nature of the starting compounds and the phosphine ligands employed was demonstrated. An unexpected spontaneous resolution upon crystallization of the macrocycle comprising anthraquinone and dioxadiamine moieties was observed while in the case of the macrocycle with a trioxadiamine linker racemic monocrystals were obtained. Crystallization of the enantiomerically enriched mixtures afforded chiral macrocycles with 88,99% ee. [source] tert -Butanesulfinylphosphines: Simple Chiral Ligands in Rhodium-Catalyzed Asymmetric Addition of Arylboronic Acids to Electron-Deficient OlefinsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 5 2010Feng Lang Abstract An efficient rhodium complex catalyst system was developed by using a class of simple tert -butanesulfinylphosphines as bidentate ligands, which solely bear sulfur chirality and combine the advantages of both sulfoxide and phosphine ligands. Excellent activities (in 0.5 hour, up to 99% yield) and enantioselectivities (up to 98% ee) were displayed in Rh-catalyzed asymmetric 1,4-additions under mild conditions. [source] Highly Selective Cobalt-Catalyzed Hydrovinylation of StyreneADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 13 2009Michiel M. Abstract Phosphine complexes of cobalt halide salts activated by diethylaluminum chloride are shown to yield highly active catalysts in the hydrovinylation of styrene, with unprecedented high selectivity to the desired product 3-phenyl-1-butene (3P1B). Double-bond isomerization, a common problem in codimerization reactions, only occurs after full conversion with these catalyst systems, even at elevated temperature. The most active catalysts are based on cobalt halide species combined with either C1 - or C2 -bridged diphosphines, heterodonor P,N or P,O ligands, flexible bidentate phosphine ligands or monodentate phosphine ligands. Kinetic investigations show an order >1 in catalyst, which indicates either the involvement of dinuclear species in the catalytic cycle or partial catalyst decomposition via a bimolecular pathway. [source] Cationic Ruthenium-Cyclopentadienyl-Diphosphine Complexes as Catalysts for the Allylation of Phenols with Allyl Alcohol; Relation between Structure and Catalytic Performance in O - vs.ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2009C -Allylation Abstract A new catalytic method has been investigated to obtain either O - or C -allylated phenolic products using allyl alcohol or diallyl ether as the allyl donor. With the use of new cationic ruthenium(II) complexes as catalyst, both reactions can be performed with good selectivity. Active cationic Ru(II) complexes, having cyclopentadienyl and bidentate phosphine ligands are generated from the corresponding Ru(II) chloride complexes with a silver salt. The structures of three novel (diphosphine)Ru(II)CpCl catalyst precursor complexes are reported. It appears that the structure of the bidentate ligand has a major influence on catalytic activity as well as chemoselectivity. In addition, a strong cocatalytic effect of small amounts of acid is revealed. Model experiments are described that have been used to build a reaction network that explains the origin and evolution in time of both O -allylated and C -allylated phenolic products. Some mechanistic implications of the observed structure vs. performance relation of the [(diphosphine)RuCp]+ complexes and the cocatalytic role of added protons are discussed. [source] ,Click' Dendritic Phosphines: Design, Synthesis, Application in Suzuki Coupling, and Recycling by NanofiltrationADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 3 2009Michèle Janssen Abstract A new synthetic route towards stable molecular-weight enlarged monodentate phosphine ligands via ,click' chemistry was developed. These ligands were applied in the Pd-catalyzed Suzuki,Miyaura coupling of aryl halides and phenyl boronic acid. The supported systems show very similar activities compared to the unsupported analogues. Moreover, recycling experiments by means of nanofiltration using ceramic nanofiltration membranes demonstrate that these systems can be recovered and reused efficiently. [source] Air-Stable and Highly Active Dendritic Phosphine Oxide- Stabilized Palladium Nanoparticles: Preparation, Characterization and Applications in the Carbon-Carbon Bond Formation and Hydrogenation ReactionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 6 2008Lei Wu Abstract Dendrimer-stabilized palladium nanoparticles were formed in the reduction of palldium bis(acetylacetonate) [Pd(acac)2] in the presence of phosphine dendrimer ligands using hydrogen in tetrahydrofuran. The resulting Pd nanoparticles were characterized by TEM, 31P,NMR and 31P MAS NMR. The results indicated that the dendritic phosphine ligands were oxidized to phosphine oxides. These dendrimer-stabilized Pd nanoparticles were demonstrated to be efficient catalysts for Suzuki and Stille coupling reactions and hydrogenations. The dendritic wedges served as a stabilizer for keeping the nanoparticles from aggregating, and as a vehicle for facilitating the separation and/or the recycling of the Pd catalyst. In the case of the Suzuki coupling reaction, these Pd nanoparticles exhibited high catalytic efficiency (TON up to 65,000) and air stability as compared with the commonly used homogeneous catalyst tetrakis(triphenylphosphine)palladium [Pd(PPh3)4]. In addition, the results obtained from the bulky dendritic substrate suggest that the Pd nanoparticles might act as reservoir of catalytically active species, and that the reaction is actually catalyzed by the soluble Pd(0) and/or Pd(II) species leached from the nanoparticle surface. [source] A Combinatorial Approach to Heterogeneous Asymmetric Aquacatalysis with Amphiphilic Polymer-Supported Chiral Phosphine-Palladium ComplexesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 12-13 2006Yukinari Kobayashi Abstract A library of amphiphlic polystyrene-poly(ethylene glycol) (PS-PEG) resin-supported chiral phosphine ligands was prepared by the split method using porous miniature reactors. A polymeric (R)-2-(diphenylphosphino)binaphthyl (MOP) ligand anchored onto the PS-PEG resin by an (S)-alanine tether unit was identified through the library-based screening to be an effective chiral ligand for the asymmetric palladium-catalyzed ,-allylic substitution under heterogeneous aqueous conditions. [source] Bulky Achiral Triarylphosphines Mimic BINAP in Ru(II)- Catalyzed Asymmetric Hydrogenation of KetonesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 9 2005Qing Jing Abstract In the present work, we report on catalysis of the enantioselective hydrogenation of ketones with Ru(II) complexes composed of cheap achiral monodentate phosphine ligands in combination with an enantiopure 1,2-diamine, affording a variety of optically active secondary alcohols with high efficiency and enantioselectivity. The steric impact of achiral monophosphine ligands in Ru complexes was found to be a critical factor for the high enantioselectivity of the reaction. This finding throws some light on a long-standing challenge, the high cost of chiral bisphosphine ligands, associated with an industrial application of the asymmetric hydrogenation of ketones. [source] The mediation of aryl ketone deuteration by [Ir(PPh3)3(cod)]+.BF4,JOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 5 2005John M. Herbert Abstract The usefulness of the hydrogen isotope exchange catalyst, [Ir(PPh3)3(cod)]+.BF4, (1), is explored. It appears that isotopic exchange mediated by 1 occurs via a series of complexes in which all three phosphine ligands are retained. The disadvantage of this system is that the catalytic intermediates are necessarily sterically hindered, with the result that the range of substrates for which the system is effective is small. Copyright © 2005 John Wiley & Sons, Ltd. [source] Ligand effects upon deuterium exchange in arenes mediated by [Ir(PR3)2(cod)]+.BF4,JOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 1 2004George J. Ellames Abstract A series of complexes of general form [Ir(PR3)2(cod)]+ has been prepared and used, without isolation, to mediate deuteration of a range of model substrates. The data suggest that, with many substrates, basicity of the phosphine ligands bound to iridium is an important factor influencing substrate selectivity and the efficiency of deuteration. In addition, the spectrum of activity of iridium complexes bearing pure donor ligands is different in many cases to that of complexes where the ligands are known to be ,-acids. Copyright © 2003 John Wiley & Sons, Ltd. [source] Controlled radical polymerization of 2-hydroxyethyl methacrylate with a hydrophilic ruthenium complex and the synthesis of amphiphilic random and block copolymers with methyl methacrylate,JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 12 2002Yusuke Fuji Abstract A hydrophilic ruthenium complex with ionic phosphine ligands {1: RuCl2[P(3-C6H4SO3Na)(C6H5)2]2} induced controlled radical polymerization of 2-hydroxyethyl methacrylate (HEMA) in methanol under homogeneous conditions; the initiator was a chloride (R-Cl) such as CHCl2COPh. The number-average molecular weights of poly(HEMA) increased in direct proportion to monomer conversion, and the molecular weight distributions were relatively narrow (Mw/Mn = 1.4,1.7). A similar living radical polymerization was possible with (MMA)2 -Cl [(CH3)2C(CO2CH3)CH2C(CH3)(CO2CH3)Cl] as an initiator coupled with amine additives such as n -Bu3N. In a similar homogeneous system in methanol, methyl methacrylate (MMA) could also be polymerized in living fashion with the R-Cl/1 initiating system. Especially for such hydrophobic polymers, the water-soluble ruthenium catalyst was readily removed from the polymers by simple washing with an aqueous dilute acid. This system can be applied to the direct synthesis of amphiphilic random and block copolymers of HEMA and MMA. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2055,2065, 2002 [source] Concomitant polymorphic behavior of di-,-thiocyanato-,2N:S;,2S:N -bis[bis(tri- p -fluorophenylphosphine-,P)silver(I)]ACTA CRYSTALLOGRAPHICA SECTION B, Issue 1 2010Bernard Omondi The structures of two polymorphs, both monoclinic P21/n [polymorph (I)] and P21/c [polymorph (II)], of di-,-thiocyanato-,2N:S;,2S:N -bis[bis(tri- p -fluorophenylphosphine-,P)silver(I)] complexes have been determined at 100,K. In both polymorphs the complex has a dinuclear structure where the silver(I) coordinates to two phosphine ligands and two bridging thiocyanate anions to form complexes with distorted tetrahedral geometry. Polymorph (I) has just one half of the [Ag2(SCN)2{P(4-FC6H4)3}4] molecule at (0, ½, 0) from the origin in the asymmetric unit. Polymorph (II) has one and a half molecules of [Ag2(SCN)2{P(4-FC6H4)3}4] in the asymmetric unit; the half molecule is situated at (0, 1, ½), while the full molecule is located at (1/3, ½, 1/3) from the origin. The Ag,P bond distances range from 2.4437,(4) to 2.4956,(7),Å in both polymorphs. The Ag,S distances are 2.5773,(7),Å in (I) and 2.5457,(5), 2.5576,(5) and 2.5576,(5),Å in (II). The full molecule in polymorph (II) has slightly shorter Ag,N bond distances [2.375,(1) and 2.367,(2),Å] compared with the half molecules in both polymorphs [2.409,(2),Å in (II) and 2.395,(2),Å in (I)]. The two polymorphs are compared using r.m.s. overlay calculations as well as half-normal probability plot analysis. [source] Biaryls Made Easy: PEPPSI and the Kumada,Tamao,Corriu ReactionCHEMISTRY - A EUROPEAN JOURNAL, Issue 1 2007Michael G. Organ Prof. Abstract An easily employed, highly versatile Kumada,Tamao,Corriu (KTC) protocol utilizing the PEPPSI (Pyridine, Enhanced, Precatalyst, Preparation, Stabilization and Initiation) precatalysts 1 and 2 is detailed. The ease-of-use of these catalysts and the synthesis of a wide range of hindered biaryls, large coupling partners and drug-like heterocycles, in high yield, makes the PEPPSI-KTC protocol very attractive. The high reactivity of the PEPPSI system allowed a tetra- ortho -substituted heterocycle, 11 to be synthesized at room temperature for the first time using any protocol. The PEPPSI protocols also tolerated the Boc protecting group and phenols required no protection in modified conditions. A relatively large scale (10 g) reaction was also performed with no loss in performance. Furthermore, PEPPSI-IPr, 1, was compared to previously reported highly active phosphine ligands 42, 43, and 44 and was shown to result in significantly better yields under identical conditions. Finally, we demonstrated that the PEPPSI catalyst system is very adept at performing sequential KTC coupling reactions, analogous to multicomponent reactions, which allow complex polyaryl and polyheteroaryl architectures to be produced in one single operation. [source] Highly Active and Removable Ruthenium Catalysts for Transition-Metal-Catalyzed Living Radical Polymerization: Design of Ligands and CocatalystsCHEMISTRY - AN ASIAN JOURNAL, Issue 8-9 2008Makoto Ouchi Dr. Abstract The systematic search and design of phosphine ligands (PR3) and amine cocatalysts resulted in obtaining pentamethyl-cyclopentadienyl (Cp*) ruthenium(II) phosphine complexes [RuCp*Cl(PR3)2], which are highly active and removable catalysts, for transition-metal-catalyzed living radical polymerization of methyl methacrylate (MMA). The catalysts are conveniently prepared in situ from a tetrameric precursor [RuCp*(,3 -Cl)]4 and a selected phosphine (PR3). The combination of the meta -tolyl phosphine [P(m -Tol)3] ligand and a primary diamine cocatalyst [NH2(CH2)6NH2] provides a highly active catalytic system with precision control of the molecular weight of the polymer. The high activity enables a low catalyst dose and a high turn-over frequency without deteriorating the controllability. A hydrophilic amine cocatalyst (amino alcohol) in place of the diamine, further forms an active and removable catalyst; simple treatment with acidic water gave colorless polymers visually free from metal residues (>97,% removal; <64,ppm). [source] | |||||||||||||||||||||||||