Home About us Contact
|
Home About us Contact | ||
|
|
||
Chelate Ligands (chelate + ligand)
Selected AbstractsPreparation of Optically Active ,-Amino[3]ferrocenophanes , Building Blocks for Chelate Ligands in Asymmetric CatalysisEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2003Patrick Liptau Treatment of 1,1,-diacetylferrocene (4) with dimethylamine and TiCl4 yielded the unsaturated dimethylamino-substituted [3]ferrocenophane product 5. Its catalytic hydrogenation gave the corresponding saturated [3]ferrocenophane system 6 (trans/cis , 7:1). The rac -[3]ferrocenophane amine 6 was partially resolved (to ca. 80% ee) by means of L - or D - O,O, -dibenzoyltartrate salt formation. Treatment of 4 with the pure (R)- or (S)-methyl(1-phenylethyl)amine (8)/TiCl4 gave the corresponding optically active unsaturated [3]ferrocenophane amines (R)-(+)- 9 and (S)-(,)- 9, respectively. Their catalytic hydrogenation again proceeded trans -selectively, giving the corresponding saturated diastereomeric [3]ferrocenophane amines (1R,3R,5R)- 10a and (1S,3S,5R)- 10b [starting from (R)- 9], their enantiomers ent - 10a and ent - 10b were obtained from (S)- 9, but with a poor asymmetric induction (10a/10b < 2:1). Quaternization of 6 (CH3I) followed by amine exchange using (R)- or (S)-methyl(1-phenylethyl)amine (8), respectively, proceeded with overall retention. Subsequent chromatographic separation gave the pure diastereoisomers (1R,3R,5R)- 10a and (1S,3S,5R)- 10b [from (R)- 8, ent - 10a and ent - 10b from (S)- 8] in > 60% yield. Subsequently, the benzylic (1-phenylethyl) auxiliary was removed from the nitrogen atom by catalytic hydrogenolysis to yield the enantiomerically pure (> 98%) ([3]ferrocenophanyl)methylamines (1R,3R)- 11 and (1S,3S)- 11, respectively, which were converted into the corresponding dimethylamino-substituted [3]ferrocenophanes (1R,3R)- 6 and (1S,3S)- 6. Each enantiomer from the following enantiomeric pairs was isolated in its pure form and characterized by X-ray diffraction: (R)- 9/(S)- 9; (1R,3R,5R)- 10a/(1S,3S,5S)- 10a; (1R,3R,5S)- 10b/(1S,3S,5R)- 10b; (1R,3R)- 11/(1S,3S)- 11. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Minocycline-Based Europium(III) Chelate Complexes: Synthesis, Luminescent Properties, and Labeling to StreptavidinHELVETICA CHIMICA ACTA, Issue 11 2009Takuya Nishioka Abstract Two chelate ligands for europium(III) having minocycline (=(4S,4aS,5aR,12aS)-4,7-bis(dimethylamino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,12,12a-tetrahydroxy-1,11-dioxonaphthacene-2-carboxamide; 5) as a VIS-light-absorbing group were synthesized as possible VIS-light-excitable stable Eu3+ complexes for protein labeling. The 9-amino derivative 7 of minocycline was treated with H6TTHA (=triethylenetetraminehexaacetic acid=3,6,9,12-tetrakis(carboxymethyl)-3,6,9,12-tetraazatetradecanedioic acid) or H5DTPA (=diethylenetriaminepentaacetic acid=N,N -bis{2-[bis(carboxymethyl)amino]ethyl}glycine) to link the polycarboxylic acids to minocycline. One of the Eu3+ chelates, [Eu3+(minocycline-TTHA)] (13), is moderately luminescent in H2O by excitation at 395,nm, whereas [Eu3+(minocycline-DTPA)] (9) was not luminescent by excitation at the same wavelength. The luminescence and the excitation spectra of [Eu3+(minocycline-TTHA)] (13) showed that, different from other luminescent EuIII chelate complexes, the emission at 615,nm is caused via direct excitation of the Eu3+ ion, and the chelate ligand is not involved in the excitation of Eu3+. However, the ligand seems to act for the prevention of quenching of the Eu3+ emission by H2O. The fact that the excitation spectrum of [Eu3+(minocycline-TTHA)] is almost identical with the absorption spectrum of Eu3+ aqua ion supports such an excitation mechanism. The high stability of the complexes of [Eu3+(minocycline-DTPA)] (9) and [Eu3+(minocycline-TTHA)] (13) was confirmed by UV-absorption semi-quantitative titrations of H4(minocycline-DTPA) (8) and H5(minocycline-TTHA) (12) with Eu3+. The titrations suggested also that an 1,:,1 ligand Eu3+ complex is formed from 12, whereas an 1,:,2 complex was formed from 8 minocycline-DTPA. The H5(minocycline-TTHA) (12) was successfully conjugated to streptavidin (SA) (Scheme,5), and thus the applicability of the corresponding Eu3+ complex to label a protein was established. [source] Evolution of iron catalysts for effective living radical polymerization: P,N chelate ligand for enhancement of catalytic performancesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 20 2008Chihiro Uchiike Abstract Iron catalysts were evolved for more active transition metal-catalyzed living radical polymerization through design of the ligands. In situ introduction of P,N chelate-ligands, consisting of hetero-coordinating atoms [phosphine (P) and nitrogene (N)], onto FeBr2 effectively catalyzed living radical polymerization of methyl methacrylate (MMA) in conjunction with a bromide initiator, where the monomer-conversion reached over 90% without dropping the rates and the molecular weights of obtained PMMAs were well controlled. The benign effects of the "hetero-chelation" were demonstrated by comparative experiments with homo-chelate ligands (P,P, N,N), model compounds of the composed coordination site, and the combinations. We successfully achieved an isolation of iron complex with a P,N ligand [FeBr2(DMDPE); DMDPE: (R)- N,N -dimethyl-1-(2-(diphenylphosphino)phenyl)-ethanamine], which was superior to the conventional catalyst [FeBr2(Pn -Bu)2] with respect to controllability and activity, especially at the latter stage. The catalyst was almost quantitatively removed by water washing after polymerization. It was also effective for living polymerization of styrene. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6819,6827, 2008 [source] Mechanistic investigations of antimony-catalyzed polycondensation in the synthesis of poly(ethylene terephthalate)JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 3 2006Faissal-Ali El-Toufaili Abstract The chemical aspects of poly(ethylene terephthalate) synthesis via the antimony-catalyzed polycondensation of hydroxy ethylene terephthalate end groups were studied to elucidate its mechanism. A polycondensation mechanism was proposed in which activation occurs by the formation of a chelate ligand on antimony composed of the hydroxyl end group and alcoholic oxygen of the ester of the same end group. The rate-determining step of the polycondensation reaction was concluded to be the coordination of a second chain end to antimony. The low activity of antimony at a high concentration of hydroxyl end groups was proposed to result from the competition between hydroxyl end groups and the chelate structure leading to the transition state. The high selectivity of antimony is probably due to its relatively low Lewis acidity. Moreover, antimony was found to stabilize hydroxyl end groups against degradation by preventing their complexation to carbonyl functionalities. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1049-1059, 2006 [source] [N,N,-Bis(salicylidene)-2,2-dimethyl-1,3-propanediaminato]nickel(II) and [N,N,-bis(salicylidene)-2,2-dimethyl-1,3-propanediaminato]copper(II)ACTA CRYSTALLOGRAPHICA SECTION C, Issue 7 2001Cengiz Arici In the title compounds, {2,2,-[2,2-dimethyl-1,3-propanediylbis(nitrilomethylidyne)]diphenolato-,4N,N,,O,O,}nickel(II), [Ni(C19H20N2O2)], and {2,2,-[2,2-dimethyl-1,3-propanediylbis(nitrilomethylidyne)]diphenolato-,4N,N,,O,O,}copper(II), [Cu(C19H20N2O2)], the NiII and CuII atoms are coordinated by two iminic N and two phenolic O atoms of the N,N,-bis(salicylidene)-2,2-dimethyl-1,3-propanediaminate (SALPD2,, C17H16N2O22,) ligand. The geometry of the coordination sphere is planar in the case of the NiII complex and distorted towards tetrahedral for the CuII complex. Both complexes have a cis configuration imposed by the chelate ligand. The dihedral angles between the N/Ni/O and N/Cu/O coordination planes are 17.20,(6) and 35.13,(7)°, respectively. [source] Great Framework Variation of Polymers in the Manganese(II) Maleate/,,,,-Diimine System: Syntheses, Structures, and Magneto-Structural CorrelationEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2003Chengbing Ma Abstract Three novel manganese(II) coordination polymers, [Mn (maleate)(phen)]n (1; phen = 1,10-phenanthroline), [Mn(maleate)(phen)]n·nH2O (2), and [Mn(maleate)(bpy)]n (3; bpy = 2,2,-bipyridine), have been synthesized by treatment of Mn2+ with maleic acid with participation of chelate diimine ligands, and have been identified by single-crystal X-ray diffraction to have either one-dimensional (1D) zigzag chain structures (1 and 2) or a two-dimensional (2D) sinuous layer structure (3). Each maleate dianion coordinates to three Mn centers, in different bridging modes (syn - anti in 1 and 2, syn - syn and anti - anti in 3). These compounds represent an interesting example of structural topology variation from 1D to 2D mediated by chemically similar auxiliary chelate ligands. Variable-temperature magnetic susceptibility measurements show weak anti-ferromagnetic exchange interactions between the adjacent MnII ions, with J = ,0.06 cm,1 (2) and J = ,1.3 cm,1, zJ, = ,0.27 cm,1 (3). The differences in the magnitudes of these coupling interactions agree well with the nature of the carboxylate-bridging coordination of maleate. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Minocycline-Based Europium(III) Chelate Complexes: Synthesis, Luminescent Properties, and Labeling to StreptavidinHELVETICA CHIMICA ACTA, Issue 11 2009Takuya Nishioka Abstract Two chelate ligands for europium(III) having minocycline (=(4S,4aS,5aR,12aS)-4,7-bis(dimethylamino)-1,4,4a,5,5a,6,11,12a-octahydro-3,10,12,12a-tetrahydroxy-1,11-dioxonaphthacene-2-carboxamide; 5) as a VIS-light-absorbing group were synthesized as possible VIS-light-excitable stable Eu3+ complexes for protein labeling. The 9-amino derivative 7 of minocycline was treated with H6TTHA (=triethylenetetraminehexaacetic acid=3,6,9,12-tetrakis(carboxymethyl)-3,6,9,12-tetraazatetradecanedioic acid) or H5DTPA (=diethylenetriaminepentaacetic acid=N,N -bis{2-[bis(carboxymethyl)amino]ethyl}glycine) to link the polycarboxylic acids to minocycline. One of the Eu3+ chelates, [Eu3+(minocycline-TTHA)] (13), is moderately luminescent in H2O by excitation at 395,nm, whereas [Eu3+(minocycline-DTPA)] (9) was not luminescent by excitation at the same wavelength. The luminescence and the excitation spectra of [Eu3+(minocycline-TTHA)] (13) showed that, different from other luminescent EuIII chelate complexes, the emission at 615,nm is caused via direct excitation of the Eu3+ ion, and the chelate ligand is not involved in the excitation of Eu3+. However, the ligand seems to act for the prevention of quenching of the Eu3+ emission by H2O. The fact that the excitation spectrum of [Eu3+(minocycline-TTHA)] is almost identical with the absorption spectrum of Eu3+ aqua ion supports such an excitation mechanism. The high stability of the complexes of [Eu3+(minocycline-DTPA)] (9) and [Eu3+(minocycline-TTHA)] (13) was confirmed by UV-absorption semi-quantitative titrations of H4(minocycline-DTPA) (8) and H5(minocycline-TTHA) (12) with Eu3+. The titrations suggested also that an 1,:,1 ligand Eu3+ complex is formed from 12, whereas an 1,:,2 complex was formed from 8 minocycline-DTPA. The H5(minocycline-TTHA) (12) was successfully conjugated to streptavidin (SA) (Scheme,5), and thus the applicability of the corresponding Eu3+ complex to label a protein was established. [source] Facile, Efficient Copolymerization of Ethylene with Bicyclic, Non-Conjugated Dienes by Titanium Complexes Bearing Bis(,-Enaminoketonato) LigandsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 10 2009Jing-yu Liu Abstract Copolymerizations of ethylene with 5-vinyl-2-norbornene or 5-ethylidene-2-norbornene under the action of various titanium complexes bearing bis(,-enaminoketonato) chelate ligands of the type, [R1NC(R2)CHC(R3)O]2TiCl2 (1, R1=Ph, R2=CF3, R3=Ph; 2, R1=C6H4F- p, R2=CF3, R3=Ph; 3, R1=Ph, R2=CF3, R3=t- Bu; 4, R1=C6H4F- p, R2=CF3, R3=t- Bu; 5, R1=Ph, R2=CH3, R3=CF3; 6, R1=C6H4F- p, R2=CH3, R3=CF3), have been shown to occur with the regioselective insertion of the endocyclic double bond of the monomer into the copolymer chain, leaving the exocyclic vinyl double bond as a pendant unsaturation. The ligand modification strongly affects the copolymerization behaviour. High catalytic activities and efficient co-monomer incorporation can be easily obtained by optimizing the catalyst structures and polymerization conditions. [source] Vinylic and ring-opening metathesis polymerization of norbornene with bis(,-ketoamine) cobalt complexes,JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 22 2005Feng Bao Abstract Cobalt complexes 1,4 bearing N,O -chelate ligands based on condensation products of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone with aniline, o -methylaniline, ,-naphthylamine, and p -nitroaniline, respectively, were synthesized, and the structures of 1 and 4 were characterized by single-crystal X-ray diffraction analyses. The bis(,-ketoamine) cobalt complexes could act as moderately active catalyst precursors for norbornene polymerization with the activation of methylaluminoxane. This catalytic reaction proceeded mainly through a vinyl-type polymerization mechanism. 1H NMR and IR showed that in all cases, a small amount of double bonds raised from ring-opening metathesis polymerization (ROMP) was present in the polymerization products. The variation of the polymerization conditions affected the ROMP unit ratio in the polynorbornenes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5535,5544, 2005 [source] FI Catalysts: new olefin polymerization catalysts for the creation of value-added polymersTHE CHEMICAL RECORD, Issue 3 2004Makoto Mitani Abstract This contribution reports the discovery and application of phenoxy,imine-based catalysts for olefin polymerization. Ligand-oriented catalyst design research has led to the discovery of remarkably active ethylene polymerization catalysts (FI Catalysts), which are based on electronically flexible phenoxy,imine chelate ligands combined with early transition metals. Upon activation with appropriate cocatalysts, FI Catalysts can exhibit unique polymerization catalysis (e.g., precise control of product molecular weights, highly isospecific and syndiospecific propylene polymerization, regio-irregular polymerization of higher ,-olefins, highly controlled living polymerization of both ethylene and propylene at elevated temperatures, and precise control over polymer morphology) and thus provide extraordinary opportunities for the syntheses of value-added polymers with distinctive architectural characteristics. Many of the polymers that are available via the use of FI Catalysts were previously inaccessible through other means of polymerization. For example, FI Catalysts can form vinyl-terminated low molecular weight polyethylenes, ultra-high molecular weight amorphous ethylene,propylene copolymers and atactic polypropylenes, highly isotactic and syndiotactic polypropylenes with exceptionally high peak melting temperatures, well-defined and controlled multimodal polyethylenes, and high molecular weight regio-irregular poly(higher ,-olefin)s. In addition, FI Catalysts combined with MgCl2 -based compounds can produce polymers that exhibit desirable morphological features (e.g., very high bulk density polyethylenes and highly controlled particle-size polyethylenes) that are difficult to obtain with conventionally supported catalysts. In addition, FI Catalysts are capable of creating a large variety of living-polymerization-based polymers, including terminally functionalized polymers and block copolymers from ethylene, propylene, and higher ,-olefins. Furthermore, some of the FI Catalysts can furnish living-polymerization-based polymers catalytically by combination with appropriate chain transfer agents. Therefore, the development of FI Catalysts has enabled some crucial advances in the fields of polymerization catalysis and polymer syntheses. © 2004 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 4: 137,158; 2004: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.20010 [source] | ||||||||||