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Metal Centers (metal + center)
Kinds of Metal Centers Selected AbstractsNon-Tethered Organometallic Phosphonate Inhibitors for Lipase Inhibition: Positioning of the Metal Center in the Active Site of Cutinase,,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 28 2008Cornelis A. Kruithof Abstract Organometallic NCN-pincer complexes, bearing either a p -nitrophenyl phosphonate ester or a phosphonic acid group directly attached to the aromatic ring of the pincer complex, were synthesized. These compounds were tested as covalent inhibitors for the lipase cutinase. In a stoichiometric reaction of the NCN-pincer platinum phosphonate p -nitrophenyl ester 2 with cutinase, a 94,% conversion to the protein,pincer metal complex hybrid was obtained in 48 h. The NCN-pincer metal phosphonic acid derivatives (3, 4) appeared to be inactive as cutinase inhibitors. In contrast to our previous work which entails propyl tethered phosphonate esters connected to pincer metal complexes, the presented strategy allows positioning of metal complexes inside the active site of lipases. This opens up the possibility for fine-tuning the chemical environment (second coordination sphere) around a synthetic metal center inside the pocket of an enzyme for diagnostic and catalytic purposes.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Can the cyclo-P5 Ligand Introduce Basicity at the Transition Metal Center in Metallocenes?CHEMINFORM, Issue 35 2004A Hybrid Density Functional Study on the cyclo-P5 Analogues of Metallocenes of Fe No abstract is available for this article. [source] Novel Bonding Modes between Tetrathiafulvalenes (TTFs) and Transition Metal Centers: ,-Bonding and Covalent TTFSiMe2,MLn Coordination to PlatinumEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2004Mathuresh N. Jayaswal Abstract Two novel strategies for coordinating TTF to transition metal centers have been developed. The reaction of tetrathiafulvalene (TTF) or 3,4-dimethyltetrathiafulvalene (o -Me2TTF) with [Pt(,2 -C2H4)(PPh3)2] leads to the , complexes [Pt(,2 -TTF)(PPh3)2] (1) and [Pt(,2 - o -Me2TTF)(PPh3)2] (2), respectively. An X-ray crystallographic study performed on 2 confirmed, that TTFs act as a , acidic ligand. NMR studies revealed the existence, in solution, of an equilibrium between free and complexed TTF. Dilithiation of o -Me2TTF and subsequent silylation with ClSiMe2H afforded 3,4-dimethyl-3,,4,-(dimethylsilyl)tetrathiafulvalene (3), which has been structurally characterized. 3 reacts by oxidative addition across [Pt(,2 -C2H4)(PPh3)2] to give [Pt{,2 - o -(SiMe2)2TTFMe2}(PPh3)2] (4), in which the TTF ligand is covalently ligated to platinum via SiMe2 bridges. The redox properties of 3 and 4 have been investigated by cyclic voltammetry. Strong cathodic shifts of the two redox processes were observed for 4, implying the TTF core. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] A Multinuclear Coordination System of L -Cysteine and L -Penicillamine That Induce Opposite Chiralities at Metal CentersANGEWANDTE CHEMIE, Issue 45 2009Yuko Sameshima Gleich und doch verschieden:L -Cystein (L -Cys) und L -Penicillamin (L -Pen) bilden die gleichen fünfkernigen AuI3M2 -Strukturen (M=NiII, CoIII) mit allerdings umgekehrten Konfigurationen. Als Ursache für dieses Phänomen werden intramolekulare Wasserstoffbrücken und sterische Wechselwirkungen vermutet, die auch erklären könnten, weshalb sich in der Natur D -Penicillamin wie L -Cystein verhält. [source] Metal,Metal Bond or Isolated Metal Centers?CHEMINFORM, Issue 11 2006Interaction of Hg(CN)2 with Square Planar Transition Metal Cyanides. 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, please click on HTML or PDF. [source] Syntheses and Crystal Structures of [Mg(HF)2](SbF6)2 and [Ca(HF)2](SbF6)2: New Examples of HF Acting as a Ligand to Metal Centers.CHEMINFORM, Issue 32 2003Alenka Turicnik Abstract For Abstract see ChemInform Abstract in Full Text. [source] Dinuclear Iridium(III) Complexes Linked by a Bis(,-diketonato) Bridging Ligand: Energy Convergence versus Aggregation-Induced EmissionEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2010Chang Hwan Shin Abstract Novel iridium(III)/iridium(III) and iridium(III)/platinum(II) dinuclear complexes, [{Ir(ppyFF)2}2(,2 - L)] (4) and [{Ir(ppyFF)2}(,2 - L){Pt(ppy)}] (5) [ppyFF = 2-(2,4-difluorophenyl)pyridine, ppy = 2-phenylpyridine, L = 1,3-bis(3-phenyl-3-oxopropanoyl)benzene], linked by an L bridging ligand were prepared, and their photophysical properties were investigated in solution and in the solid state. The photophysical properties of mononuclear iridium(III) and platinum(II) complexes, [Ir(ppyFF)2(dbm)] (1) and [Pt(ppy)(dbm)] (2) bearing a dibenzoylmethane (dbm) ligand were also compared. Whereas the UV/Vis absorption spectra of 4 and 5 show independent light absorption at each metal-centered moiety, the photoluminescence spectra of 4 and 5 display almost identical features, but very weak emissions in solution at both room temperature and 77 K. The weak emission in solution is found to mainly originate from a 3LX state of the L bridging ligand, which reflects the occurrence of efficient energy convergence from the triplet states of the Pt(ppy) and Ir(ppyFF) moieties to the 3LX state of L. By contrast, intense orange-red emission, that is, aggregation-induced emission, is produced in the solid state of 4 and 5. Inspection of the crystal-packing structures of 5 reveals that strong intermolecular ,,, interactions between the adjacent pyridine rings of ppyFF ligands in the Ir-centered moieties are responsible for the emissive metal-to-ligand,ligand charge-transfer [3M(LL)CT] state of the solid-state dinuclear systems. The electrochemical properties of 4 and 5 further indicate that the first two reductions occur at the dbm moieties of the L bridging ligand linked to each metal center, which is consistent with the fact that the lowest-energy excited state of the L bridging ligand dominates the excited-state properties of 4 and 5 in solution. [source] Synthesis, Characterization, and Protonation Reactions of Ar-BIAN and Ar-BICAT Diimine Platinum Diphenyl ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2010Jerome Parmene Abstract PtII diphenyl complexes (N,N)PtPh2 [N,N = diimines Ar,N=C(An)C=N,Ar with Ar = substituted aryl groups] have been prepared and characterized by 1H, 13C, and 195Pt NMR spectroscopy. The 195Pt NMR spectroscopic data establish the electronic influence exerted by substituents at the backbone of the diimine ligand system to the metal center. When compared to diimines Ar,N=CMe,CMe=N,Ar, the electron-withdrawing ability of the Ar-BIAN ligand and the electron-donating ability of the O,O-heterocyclic Ar-BICAT systems are demonstrated. Trends in 195Pt NMR chemical shifts suggest that electronic tuning of the metal center is better achieved through variations of the diimine backbone substituents rather than variation of the substituents at the N-Aryl groups. Protonation of (N,N)PtPh2 in dichloromethane/acetonitrile at ,78 °C furnishes the corresponding PtIV hydrides (N,N)PtPh2H(NCMe)+. The PtIV hydrides liberate benzene with the formation of (N,N)PtPh(NCMe)+ when the temperature is raised. A second protonation and rapid benzene elimination produces the dicationic PtII species (N,N)Pt(NCMe)22+ at approximately 50 °C. Protonation of (N,N)PtPh2 in the absence of acetonitrile results in the clean formation of (N,N)PtPh(,2 -C6H6)+ at temperatures that depend on the steric hindrance provided by the alkyl substituents at the diimine N-aryl groups. These findings support the notion that the metal is the kinetically preferred site of protonation. The results qualitatively agree with a recent mechanistic study of protonation-induced reactions of (diimine)PtPh2 complexes that bear simple methyl substituents at the diimine backbone. Several compounds have been crystallographically characterized. All complexes have the expected square planar environment at the metal. Modest variations in the metric parameters suggest that the Ar-BICAT system has a weaker trans influence than the Ar-BIAN and Ar-DAB systems. [source] Non-Tethered Organometallic Phosphonate Inhibitors for Lipase Inhibition: Positioning of the Metal Center in the Active Site of Cutinase,,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 28 2008Cornelis A. Kruithof Abstract Organometallic NCN-pincer complexes, bearing either a p -nitrophenyl phosphonate ester or a phosphonic acid group directly attached to the aromatic ring of the pincer complex, were synthesized. These compounds were tested as covalent inhibitors for the lipase cutinase. In a stoichiometric reaction of the NCN-pincer platinum phosphonate p -nitrophenyl ester 2 with cutinase, a 94,% conversion to the protein,pincer metal complex hybrid was obtained in 48 h. The NCN-pincer metal phosphonic acid derivatives (3, 4) appeared to be inactive as cutinase inhibitors. In contrast to our previous work which entails propyl tethered phosphonate esters connected to pincer metal complexes, the presented strategy allows positioning of metal complexes inside the active site of lipases. This opens up the possibility for fine-tuning the chemical environment (second coordination sphere) around a synthetic metal center inside the pocket of an enzyme for diagnostic and catalytic purposes.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Facile Formation of Hexacyclic [Al3O2Cl] Aluminum and Alkoxide-Bridged Titanium Complexes: Reactions of AlMe3 with [Ti(L)Cl2] [L = 2,2,-Methylenebis(6- tert -butyl-4-methylphenolato)]EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2007Dao Zhang Abstract The titanium dichloride complex [(L)TiCl2] [L = 2,2,-methylenebis(6- tert- butyl-4-methylphenolato)] (1) reacted with trimethylaluminum (AlMe3) in a 1:2 ratio to give a trimetallic aluminum complex of the composition [(L)(AlMe2)3(,-Cl)] (2) with a symmetric six-membered ring [Al3(,2 -O)2(,2 -Cl)] and a four-coordinate aluminum center in the solid state. The reaction of 1 equiv. AlMe3 gave [(L)TiMeCl] (3), which could absorb O2 gas to afford the oxygen-insertion product [{(L)TiCl}2(,-OMe)2] (4) with a five-coordinate metal center. Upon reaction of H2L with AlMe3, the binuclear, four-coordinate adduct [{(L)AlMe}2] (5) was formed. Complex 4 supported on MgCl2 and activated with aluminum alkyls reveals high catalytic activity for ethylene polymerization to produce polymers with molecular weight distributions of ca. 3.1. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Tagging (Arene)ruthenium(II) Anticancer Complexes with Fluorescent LabelsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2007Fabio Zobi Abstract Fluorescent (arene)ruthenium(II) complexes have been prepared by tagging a small fluorogenic reporter onto the chelating ligand of complexes of the type [(,6 -arene)RuCl(Z)]+ (Z = chelating ligand). Complexes [(,6 - p -cym)RuCl(NNO)](Cl) (2), [(,6 - p -cym)RuCl(L3)](Cl) (3) and [(,6 - p -cym)RuCl(L4)](Cl) (4) {p -cym = p- cymene, NNO = 2-[(2-aminoethyl)amino]ethanol, L3 = 2-[(2-aminoethyl)amino]ethyl-2-(methylamino)benzoate and L4 = N -{2-[(2-aminoethyl)amino]ethyl}-2-(methylamino)benzamide} were obtained in good yield from the reaction of the Ru dimer [(,6 - p -cym)RuCl2]2 (1) and the corresponding ligand. The compounds have been fully characterized and their X-ray crystal structures are reported. Compounds 3 and 4 show a photoluminescence response centered at 435 nm with partial fluorescence quenching of the fluorogenic reporters L3 and L4 upon coordination to the metal center. Species 2,4 show good solubility both in water and organic solvents. In water, 2,4 readily hydrolyze to form the aqua complexes. These are stable at acidic pH forming 10,15,% of the corresponding hydroxido complexes in buffered solution (25 mM HEPES) as the pH is raised to a physiological value (pH = 7.44). Under these conditions, 4 (but not 2 or 3) undergoes a fast pH-dependent reversible intramolecular rearrangement. Experimental data and semiempirical calculations indicate that the major species arising from this transformation is a complex with a tridentate chelating ligand following deprotonation at the nitrogen atom of the amide group. Esterase-catalyzed hydrolysis of 3 liberates isatoic acid (MIAH) and generates 2 indicating that the complex is a substrate for the enzyme. Complexes similar to 3 may have potential for esterase-activated Ru-based prodrug delivery systems.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] N -(Aryl)picolinamide Complexes of Ruthenium: Usual Coordination and Strategic CyclometalationEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2007Sumon Nag Abstract Reaction of five N -(4- R -phenyl)picolinamides (R = OCH3, CH3, H, Cl, and NO2) with [Ru(PPh3)2(CO)2Cl2] in refluxing 2-methoxyethanol in the presence of a base (NEt3) affords two geometrical isomers of a group of complexes (1-R and 2-R), each of which contains an amide ligand coordinated to the metal center as a monoanionic bidentate N,N donor along with two triphenylphosphanes, a carbonyl, and a hydride. Similar reaction of N -(naphthyl)picolinamide with [Ru(PPh3)2(CO)2Cl2] affords an organometallic complex, 3, in which the amide ligand is coordinated to the metal center, by C,H activation of the naphthyl ring at the 8-position, as a dianionic tridentate N,N,C donor along with two triphenylphosphanes and one carbonyl. Structures of the 1-OCH3, 2-CH3, and 3 complexes have been determined by X-ray crystallography. In all the complexes the two triphenylphosphanes are trans. In the 1-R complexes the hydride is trans to the pyridine nitrogen and in the 2-R complexes it is trans to the amide-nitrogen. All the complexes are diamagnetic, and show characteristic 1H NMR signals and intense MLCT transitions in the visible region. Cyclic voltammetry on all the complexes shows a RuII,RuIII oxidation within 0.71,0.93 V versus SCE. An oxidation and a reduction of the coordinated amide ligand are also observed within 1.29,1.69 V versus SCE and ,1.02 to ,1.21 V versus SCE respectively.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Electronic Control of the Rotational Barrier in ,2 -Alkyne-1-thio ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 7 2007Wolfram W. Seidel Abstract A family of thio-alkyne complexes [Tp,Mo(CO)(L)(BnSC2S)] {Bn = benzyl, Tp, = hydrotris(3,5-dimethylpyrazolyl)borate, L = carbonyl (2), 2,6-dimethylphenyl isocyanide (7), tert -butyl isocyanide (8), 4-(dimethylamino)pyridine (9)} was prepared by reductive removal of a benzyl group in the corresponding bis(benzylthio)acetylene complexes [Tp,Mo(CO)(L)(BnSC2SBn)](PF6) (1 -PF6, 4 -PF6, 5 -PF6 and 6 -PF6). All complexes were characterized by IR, 1H, 13C spectroscopy and cyclic voltammetry. X-ray diffraction studies of 5 -PF6, 8 and 9 were carried out. The alkyne ligand is bound symmetrically to molybdenum in 5 -PF6 and unsymmetrically in 8 and 9. The trend in the ,-acidity of ligand L is reflected in the spectroscopic and electrochemical data as well as in the molecular structures. Variable temperature 1H NMR investigations with 7, 8 and 9 disclosed that the barrier of the alkyne rotation at molybdenum decreases in the order of rising electron density at the metal center while the steric demand increases. Therefore, electronic control of the barrier by the specific character of the ligand L is evident.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Highly Symmetrical Tetranuclear Cluster Complexes Supported by p - tert -Butylsulfonylcalix[4]arene as a Cluster-Forming LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2006Takashi Kajiwara Abstract Square-planar tetranuclear clusters [M4(L)(AcO)4(,4 -OH)], (M = MnII, CoII, and NiII) are synthesized using tetra-anionic p - tert -butylsulfonylcalix[4]arene (L4,) as a cluster-forming ligand. Three complexes are crystallographically isostructural, being crystallized in the triclinic crystal system with space group P. The calix[4]arene acts as a tetrakis fac -tridentate ligand through four phenoxo and four sulfonyl oxygen atoms to form square arrangement of four metal ions, which are further bridged by four chelating acetate ions and one hydroxo ion in a ,4 manner to complete the hexacoordination of each metal center. Although the whole molecule of each complex is crystallographically independent, the molecule is highly symmetrical with a pseudo-four-fold axis lying on the ,4 -OH, group. The tetranuclear clusters are stable enough to maintain the core structures even in highly dilute solution (,10 ,M), which was confirmed by mass spectroscopic study, however, bridging acetates were easily exchanged by other carboxylate chelates to form derivatives such as [M4(L)(BzO)4(OH)],. Metal,metal interactions were investigated by means of magnetic susceptibility, and it was revealed that both ferro- and antiferromagnetic interactions occur in the NiII complex depending on the bridging angles of Ni,O,Ni. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Comparative Electrochemical Study of Unsubstituted and Substituted Bis(phthalocyaninato) Rare Earth(III) ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 3 2004Peihua Zhu Abstract The electrochemistry of homoleptic substituted phthalocyaninato rare earth double-decker complexes M(TBPc)2 and M(OOPc)2 [M = Y, La...Lu except Pm; H2TBPc = 3(4),12(13),21(22),30(31)-tetra- tert -butylphthalocyanine, H2OOPc = 3,4,12,13,21,22,30,31-octakis(octyloxy)phthalocyanine] has been comparatively studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in CH2Cl2 containing 0.1 M tetra- n -butylammonium perchlorate (TBAP). Two quasi-reversible one-electron oxidations and three or four quasi-reversible one-electron reductions have been revealed for these neutral double-deckers of two series of substituted complexes, respectively. For comparison, unsubstituted bis(phthalocyaninato) rare earth analogues M(Pc)2 (M = Y, La...Lu except Pm; H2Pc = phthalocyanine) have also been electrochemically investigated. Two quasi-reversible one-electron oxidations and up to five quasi-reversible one-electron reductions have been revealed for these neutral double-decker compounds. The three bis(phthalocyaninato)cerium compounds display one cerium-centered redox wave between the first ligand-based oxidation and reduction. The half-wave potentials of the first and second oxidations and first reduction for double-deckers of the tervalent rare earths depend on the size of the metal center. The difference between the redox potentials of the second and third reductions for MIII(Pc)2, which represents the potential difference between the first oxidation and first reduction of [MIII(Pc)2],, lies in the range 1.08,1.37 V and also gradually diminishes along with the lanthanide contraction, indicating enhanced ,,, interactions in the double-deckers connected by the smaller, lanthanides. This corresponds well with the red-shift of the lowest energy band observed in the electronic absorption spectra of reduced double-decker [MIII(Pc,)2], (Pc, = Pc, TBPc, OOPc). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Coordination Modes of 9-Methyladenine in cis -Platinum(II) Complexes with Dimethyl(phenyl)phosphanes as Ancillary Ligands , Synthesis and Characterization of cis -[PtL2(9-MeAd)2](NO3)2, cis -[PtL2{9-MeAd(,H)}]3(NO3)3, and cis -[L2Pt{9-MeAd(,H)}PtL2](NO3)3EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2003Bruno Longato Abstract Treatment of 9-methyladenine (9-MeAd) with cis -[PtL2(NO3)2] (1) (L = PMe2Ph) in a 2:1 molar ratio generated the bis(adduct) cis -[PtL2(9-MeAd)2](NO3)2 (2), which was isolated and fully characterized by multinuclear (1H, 31P, 13C, 195Pt and 15N) NMR analysis, which showed that the two nucleobases are selectively coordinated through the N1 atom. Small amounts of a mono(adduct) cis -[PtL2(S)(9-MeAd)]2+ (3) (S = solvent) and of a diplatinated species cis -[L2Pt(S){9-MeAd(,H)}PtL2]3+ (4) are formed in DMSO solution when 9-MeAd is present in smaller quantities than 1. Complex 3 is platinated at N1, with a solvent molecule representing the fourth ligand around the metal center. Complex 4 contains an adenine molecule deprotonated and platinated at N1,N6,N7, with two cis -L2Pt units bonded to nitrogen atom N1 and to nitrogen atoms N6 and N7, respectively. With increasing relative concentration of the nucleobase, both complexes 3 and 4 progressively convert into the bis(adduct) 2, the only species detectable in solution when the Ad/Pt molar ratio is 2:1. The trinuclear compound cis -[L2Pt{9-MeAd(,H)}]3(NO3)3 (5) (L = PMe2Ph), containing an NH2 -deprotonated nucleobase bridging the metal centers through the N1 and N6 atoms, is quantitatively formed when the dinuclear hydroxo complex cis -[Pt(,-OH)L2]2(NO3)2 (6) reacts with 9-MeAd in CH3CN solution. The isolated complex was fully characterized by multinuclear NMR spectroscopy and mass spectrometry. It appears to be stable in solution in CH3CN and chlorinated solvents, whereas in DMSO it partially converts into a new species, probably the dinuclear analog cis -[PtL2{9-MeAd(,H)}]2(NO3)2, in which the adenine maintains its coordination mode. At equilibrium the trinuclear/dinuclear species molar ratio is 20:1. Through the addition of a stoichiometric amount of nitrate 1 to a DMSO solution of 5 we were able to generate the diplatinated compound 4 in high yield. Complex 4 displays a new coordination mode for the adeninate ion, with N1 bonded to one platinum atom whereas N6 and N7 are chelated to a second one. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Electroactive Films of Multicomponent Building Blocks,ADVANCED FUNCTIONAL MATERIALS, Issue 5 2007I. Yildiz Abstract A ligand consisting of a 2,2,-bipyridine core and two 4,4,-bipyridinium arms terminated by a thiol group is prepared following a multistep synthetic procedure. Two of these ligands assemble around a single CuI center as a result of the tetrahedral coordination of their 2,2,-bipyridine cores by the metal. Both the ligand and the complex adsorb spontaneously on the surface of polycrystalline-gold electrodes. The surface coverage of the films prepared by immersing a gold substrate into a solution of the ligand increases from monolayer to multilayer values with immersion time. Instead, the complex can only form monolayers. The cyclic voltammograms of the resulting films show the characteristic response for the reversible reduction of the 4,4,-bipyridinium dications to their radical cations. In the case of the complex, a wave for the monoelectronic oxidation of the metal center can also be observed. The back reduction wave, however, is markedly broader and appears at significantly lower potentials. Model studies in solution indicate that this response is a result of the presence of free thiol groups and is consistent with a change in the coordination geometry of the metal. Specifically, the oxidation of the CuI center to a CuII ion is, presumably, accompanied by the folding of one of the thiol groups back to interact with the metal. Thus, oxidation/reduction cycles of the metal center can, in principle, be exploited to control reversibly large amplitude molecular motions at the electrode/solution interface in the shape of the folding/unfolding of oligomethylene chains. [source] Tuning the Energy Level and Photophysical and Electroluminescent Properties of Heavy Metal Complexes by Controlling the Ligation of the Metal with the Carbon of the Carbazole Unit,ADVANCED FUNCTIONAL MATERIALS, Issue 4 2007L. Yang Abstract Four novel IrIII and PtII complexes with cyclometalated ligands bearing a carbazole framework are prepared and characterized by elemental analysis, NMR spectroscopy, and mass spectrometry. Single-crystal X-ray diffraction studies of complexes 1, 3, and 4 reveal that the 3- or 2-position C atom of the carbazole unit coordinates to the metal center. The difference in the ligation position results in significant shifts in the emission spectra with the changes in wavelength being 84,nm for the Ir complexes and 63,nm for the Pt complexes. The electrochemical behavior and photophysical properties of the complexes are investigated, and correlate well with the results of density functional theory (DFT) calculations. Electroluminescent devices with a configuration of ITO/NPB/CBP:dopant/BCP/AlQ3/LiF/Al can attain very high efficiencies. [source] Binding Studies of Asymmetric Pentacoordinate Copper(II) Complexes Containing Phenanthroline and Ethane-1,2-diamine Ligands with Calf-Thymus DNAHELVETICA CHIMICA ACTA, Issue 9 2005Farukh Arjmand New chiral complexes of the composition [MLL,], where HL=1,2-bis(1H -benzimidazol-2-yl)ethane-1,2-diol=H2bimedol, M=CoII, NiII, CuII, and L,=1,10-phenanthroline (phen) or ethane-1,2-diamine (en), were synthesized and characterized. The ligand L exhibited a coordination mode involving the O-atom of only one OH group, the other one being directed away from the metal center. The complexes [Cu(Hbimedol)(en)]Cl (1), [Cu(Hbimedol)(phen)]Cl (2), [Co(Hbimedol)(phen)]Cl (3), [Ni(Hbimedol)(en)]Cl (4), and [Ni(Hbimedol)(phen)]Cl (5) were ionic in nature and stable at room temperature. The donor sets involved in coordination with the metal ions were the O-atom of one OH group and two N-atoms of the two benzimidazole moieties, besides the two N-atoms of phen or en (Fig.,1.). The proposed five-coordinate geometry of 1,5 was established by analysis of spectroscopic data; the ball-and-stick models supported the proposed structures of 1,5 since they showed apparently no strain on any bond and angle. The interaction of complexes 1 and 2 with calf-thymus DNA were carried out by UV/VIS titration, circular dichroism, electrochemical methods, and viscometry. The intrinsic binding constant Kb of 1 and 2 was determined as 1.57,104 and 1.51,104,M,1, respectively, suggesting that both complexes bind strongly to calf-thymus DNA. [source] Structure, Characterization, and Metal-Complexation Properties of a New Tetraazamacrocycle Containing Two Phenolic Pendant ArmsHELVETICA CHIMICA ACTA, Issue 10 2004Xiuling Cui The new tetraazamacrocycle 2 (=2,2,-[[7-Methyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),13,15-triene-3,11-diyl]bis(methylene)]bis(4-bromophenol)) was synthesized and used as a ligand for different metal-ion complexes. The X-ray crystal structures of the complexes of the general formula [M(H- 2)]+NO,MeOH (M=Ni2+, Zn2+), in which only one of the two pendant phenolic OH groups of 2 is deprotonated, were determined. In both complexes, the coordination environment is of the [5+1] type, the four N-atoms of the macrocyclic framework defining a square-planar arrangement around the metal center, with similar NiN and ZnN distances of 1.961(9) to 2.157(9),Å and 2.021(9) to 2.284(8),Å, respectively. In contrast, the MO distances are markedly different, 2.060(6) and 2.449(8),Å in the NiII complex, and 2.027(7) and 2.941(9),Å in the ZnII complex. The UV/VIS spectra of the NiII and CuII complexes with ligand 2, and the EPR spectra of the CuII system, suggest the same type of structure for the complexes in solution as in the solid state. Theoretical studies by means of density functional theory (DFT) confirmed the experimental structures of the NiII and ZnII complexes, and led to a proposal of a similar structure for the corresponding CuII complex. The calculated EPR parameters for the latter and comparison with related data support this interpretation. The singly occupied molecular orbital (SOMO) in these systems is mainly made of a d orbital of Cu, with a strong antibonding (,*) contribution of the axially bound phenolate residue. [source] Kinetic and mechanistic investigation into the influence of chelate substituents on the substitution reactions of platinum(II) terpyridine complexesINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 12 2008Deogratius Jaganyi The substitution kinetics of the complexes [Pt{4,-(o -CH3 -Ph)-terpy} Cl]SbF6 (CH3PhPtCl(Sb)), [Pt{4,-(o -CH3 -Ph)-terpy}Cl]CF3SO3 (CH3PhPtCl(CF)), [Pt(4,-Ph-terpy)Cl]SbF6 (PhPtCl), [Pt(terpy)Cl]Cl·2H2O (PtCl), [Pt{4,-(o -Cl-Ph)-terpy}Cl]SbF6 (ClPhPtCl), and [Pt{4,-(o -CF3 -Ph)-terpy}Cl]SbF6 (CF3PhPtCl), where terpy is 2,2,:6,,2,-terpyridine, with the nucleophiles thiourea (TU), N,N,-dimethylthiourea (DMTU), and N,N,N,,N,-tetramethylthiourea (TMTU) were investigated in methanol as a solvent. The substitution reactions of the chloride displacement from the metal complexes by the nucleophiles were investigated as a function of nucleophile concentration and temperature under pseudo-first-order conditions using the stopped-flow technique. The reactions followed the simple rate law kobs = k2[Nu]. The results indicate that the introduction of substituents in the ortho position of the phenyl group on the ancillary ring of the terpy unit does influence the extent of ,-backbonding in the terpy ring. This controls the electrophilicity of the platinum center, which in turn controls the lability of the chloro-leaving group. The strength of the electron-donating or -withdrawing ability of the substituents correlates with the reactivity of the complexes. Electron-donating substituents decrease the rate of substitution, whereas electron-withdrawing substituents increase the rate of substitution. This was supported by DFT calculations at the B3LYP/LACVP+** level of theory, which showed that most of the electron density of the HOMO is concentrated on the phenyl ligand rather than on the metal center in the case of the strongest electron-withdrawing substituent in CF3PhPtCl. The opposite was found to be true with the strongest electron-donating substituent in CH3PhPtCl. Thiourea was found to be the best nucleophile with N,N,N,,N,-tetramethylthiourea being the weakest due to steric effects. The temperature dependence studies support an associative mode of activation. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 808,818, 2008 [source] Kinetics and mechanism of oxidation of the drug mephenesin by bis(hydrogenperiodato)argentate(III) complex anionINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 8 2007Shigang Shen Mephenesin is being used as a central-acting skeletal muscle relaxant. Oxidation of mephenesin by bis(hydrogenperiodato)argentate(III) complex anion, [Ag(HIO6)2]5,, has been studied in aqueous alkaline medium. The major oxidation product of mephenesin has been identified as 3-(2-methylphenoxy)-2-ketone-1-propanol by mass spectrometry. An overall second-order kinetics has been observed with first order in [Ag(III)] and [mephenesin]. The effects of [OH,] and periodate concentration on the observed second-order rate constants k, have been analyzed, and accordingly an empirical expression has been deduced: k, = (ka + kb[OH,])K1/{f([OH,])[IO,4]tot + K1}, where [IO,4]tot denotes the total concentration of periodate, ka = (1.35 ± 0.14) × 10,2M,1s,1 and kb = 1.06 ± 0.01 M,2s,1 at 25.0°C, and ionic strength 0.30 M. Activation parameters associated with ka and kb have been calculated. A mechanism has been proposed to involve two pre-equilibria, leading to formation of a periodato-Ag(III)-mephenesin complex. In the subsequent rate-determining steps, this complex undergoes inner-sphere electron transfer from the coordinated drug to the metal center by two paths: one path is independent of OH, whereas the other is facilitated by a hydroxide ion. In the appendix, detailed discussion on the structure of the Ag(III) complex, reactive species, as well as pre-equilibrium regarding the oxidant is provided. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 440,446, 2007 [source] Copper-catalyzed phosphinidene transfer to ethylene, acetylene, and carbon monoxide: A computational studyINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 9 2010Matthew J. Amme Abstract A DFT study of phosphinidene transfer by copper model catalysts is reported. PR-transfer pathways are highly exergonic with respect to catalyst and phosphinidene transfer reagent. Calculated free energy barriers by which (dhpe)Cu(PMe) active species yields functionalized products are reasonable for modeled substrates,ethylene, acetylene, and carbon monoxide. Calculations suggest a (dhpe)CuI(-PMe·,) formulation as more appropriate than (dhpe)CuII(=PMe2,). The preferred pathway for production of phosphirane (phosphirene) is via direct [1 + 2] addition of ethylene (acetylene) to the PMe group of (dhpe)Cu(PMe), which contrasts the [2 + 2] mechanism for the reaction of ethylene with Ni0 -phosphinidenes. In light of simulations for neutral and cationic models, it is concluded that the extra electron in copper destabilizes [2 + 2] pathways. Calculated energetics for (dhpe)Cu(PMe) versus (en)Cu(PMe), dhpe = 1,2- bis(dihydrophosphino)ethane, en = ethylenediamine, indicate that the former is a more potent for PR-transfer. Thus, it is inferred that modifications that result in a more electron deficient metal center will yield better group transfer catalysts. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] Poly(trimethylene carbonate) from Biometals-Based Initiators/Catalysts: Highly Efficient Immortal Ring-Opening Polymerization ProcessesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 9 2009Marion Helou Abstract The ring-opening polymerization (ROP) of trimethylene carbonate (TMC) was evaluated in bulk at 60,110,°C using various catalyst systems based on bio-friendly metals, including the metal bis(trimethylsilylamides) Mg[N(SiMe3)2]2, Ca[N(SiMe3)2]2(THF)2, Y[N(SiMe3)2]3, (BDI)Fe[N(SiMe3)2] [BDI=CH(CMeNC6H3 -2,6- i- Pr2)2], Fe[N(SiMe3)2]2, Fe[N(SiMe3)2]3, Zn[N(SiMe3)2]2, (BDI)Zn[N(SiMe3)2] and ZnEt2, associated with an alcohol such as isopropyl or benzyl alcohol. The actual metal alkoxide initiating species has been formed in situ prior to the addition of TMC. Introduction of the alcohol component in excess leads to the "immortal" ring-opening polymerization (ROP) of TMC. According to such an "immortal" ROP process of TMC, whichever the metal species, as many as 200 polycarbonate chains could be successfully grown from a unique metal center in a well controlled ROP process. The best performances were obtained using the discrete (BDI)Zn[N(SiMe3)2] precursor. Under optimized conditions, as many as 50,000 equivalents of TMC could be fully converted from as little as 20,ppm of this metallic precursor, allowing the preparation of a polytrimethylene carbonate (PTMC) with a molar mass as high as 185,200,g,mol,1 with a relatively narrow molar mass distribution (Mw/Mn=1.68). A double monomer feed experiment carried out with the (BDI)Zn[N(SiMe3)2]/BnOH initiating system proved the "living" character of the polymerization. Characterization of the PTMCs by NMR and size exclusion chromatography (SEC) showed well-defined ,-hydroxy-,-alkoxycarbonate telechelic polymers, highlighting the controlled character of this "living and immortal" ROP process. Using the (BDI)Zn[N(SiMe3)2] precursor, varying the alcohol (ROH) to 2-butanol, 3-buten-2-ol or 4-(trifluoromethyl)benzyl alcohol, revealed the versatility of this approach, allowing the preparation of accordingly end-functionalized HO-PTMC-OR polymers. The very low initial loading of metal catalyst considerably limits the potential toxicity and thus allows such polycarbonates to be used in the biomedical field. [source] A Density Functional Study of Ethylene Insertion into the M-methyl (M = Ti, Zr) Bond for Different Catalysts, with a QM/MM Model for the Counterion, B(C6F5)3CH3,ISRAEL JOURNAL OF CHEMISTRY, Issue 4 2002Kumar Vanka Single site homogeneous catalysts have been studied extensively in recent years as alternatives to traditional heterogeneous catalysts. The current theoretical study uses density functional theory to study the insertion process of the ethylene monomer into the titanium-carbon chain for contact ion-pair systems of the type [L1L2TiCH3 -,-CH3 -B(C6F5)3], where L1, L2, are Cp, NPH3, and other ligands. Different modes of approach cis and trans to the ,-CH3 bridge were considered. The counterion, B(C6F5)3CH3,, was modeled by QM/MM methods. The value of ,Htot,the total barrier to insertion,was found to be positive (in the range of 4,15 kcal/mol). The ability of the ancillary ligands, L1 and L2, to stabilize the ion-pair was found to be an important factor in determining the value of ,Htot. On replacing the titanium metal center with zirconium, the ,Htot values were found to be lowered (in the range of 2,9 kcal/mol), indicating that they would be better catalysts than their titanium analogues. The size of the ligands L1 and L2 was increased by replacing hydrogens in the ligands with tertiary butyl groups. The value of ,Htot was found to increase (in the range of 10,28 kcal/mol) in contrast to the simple systems, for both the cis and trans cases of approach, with the cis mode of approach giving lower values of ,Htot. Solvent effects were incorporated with cyclohexane (, = 2.023) as the solvent, and were found to have a minor influence, ±(0.5,1.5) kcal/mol) on the insertion barrier for all the cases studied. [source] Energetic and topological analysis of the reaction of Mo and Mo2 with NH3, C2H2, and C2H4 moleculesJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 13 2004Maria Del Carmen Michelini Abstract The Density functional theory has been applied to characterize the structural features of Mo1,2NH3,C2H4, and C2H2 compounds. Coordination modes, geometrical structures, and binding energies have been calculated for several spin multiplets. It has been shown that in contrast to the conserved spin cases (Mo1,2NH3), the interaction between Mo (or Mo2) and C2H4 (or C2H2) are the low-spin (MoC2H4 and C2H2) and high-spin (Mo2C2H4 and C2H2) complexes. In the ground state of Mo1,2C2H4 and C2H2, the metal-center always reacts with the CC center. The spontaneous formation of the global minima is found to be possible due to the crossing between the potential energy surfaces (ground and excited states with respect to the metallic center). The bonding characterization has been performed using the topological analysis of the Electron Localization Function. It has been shown that the most stable electronic structure for a ,-acceptor ligand correlates with a maximum charge transfer from the metal center to the CC bond of the unsaturated hydrocarbons, resulting in the formation of two new basins located on the carbon atoms (away from hydrogen atoms) and the reduction of the number of attractors of the CC basin. The interaction between Mo1,2 and C2H4 (or C2H2) should be considered as a chemical reaction, which causes the multiplicity change. Contrarily, there is no charge transfer between Mo1,2 and NH3, and the partners are bound by an electrostatic interaction. © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 1647,1655, 2004 [source] Applications of deuterium isotope effects for probing aspects of reactions involving oxidative addition and reductive elimination of H,H and C,H bonds,JOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 11-12 2007Gerard Parkin Abstract The various types of deuterium isotope effects that are observed for reactions involving oxidative addition and reductive elimination reactions of H,H and C,H bonds with a transition metal center are reviewed. Copyright © 2007 John Wiley & Sons, Ltd. [source] Long-lived layered silicates-immobilized 2,6-bis(imino)pyridyl iron (II) catalysts for hybrid polyethylene nanocomposites by in situ polymerization: Effect of aryl ligand and silicate modificationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 2 2009Giuseppe Leone Abstract Heterogeneous-layered silicate-immobilized 2,6-bis(imino)pyridyl iron (II) dichloride/MMAO catalysts, in which the active polymerization species are intercalated within sodium- and organomodified-layered silicate galleries, were prepared for producing hybrid exfoliated polyethylene (PE) nanocomposites by means of in situ polymerization. The inorganic filler was first treated with modified-methylaluminoxane (MMAO) to produce a supported cocatalyst: MMAO reacts with silicates replacing most of the organic surfactant, thus modifying the original crystallographic clay order. MMAO anchored to the nanoclay was able to activate polymerization iron complexes initiating the polymer growth directly from the filler lamellae interlayer. The polymerization mechanism taking place in between the montmorillonite lamellae separates the layers, thus promoting deagglomeration and effective clay dispersion. Transmission electron microscopy revealed that in situ polymerization by catalytically active iron complexes intercalated within the lower organomodified clay led to fine dispersion and high exfoliation extent. The intercalated clay catalysts displayed a longer polymerization life-time and brought about ethylene polymerization more efficiently than analogous homogeneous systems. PEs having higher molecular masses were obtained. These benefits resulted to be dependent more on the filler nature than on the ligand environment around the iron metal center and the experimental synthetic route. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 548,564, 2009 [source] Photoreduction of iron protoporphyrin IX chloride in non-ionic triton X-100 micelle studied by electronic absorption and resonance Raman spectroscopyJOURNAL OF RAMAN SPECTROSCOPY, Issue 3 2001P. K. Shantha Resonance Raman and electronic absorption studies of iron protoporphyrin IX chloride (hemin) in non-ionic Triton X-100 micelle in the absence and presence of hindered imidazole (2-methylimidazole and 1,2-dimethylimidazole) and unhindered imidazole under various experimental conditions are reported. Hemin undergoes photoreduction at the metal center, both in the absence and presence of hindered imidazole, in anaerobic, alkaline and neutral pH conditions on photoexcitation by laser radiation at 441.6 and 457.9 nm. It is inferred from this study that only the monomer hemin encapsulated within the micelle under the alkaline pH conditions is photoreducible. The photoreduction of hemin in this micelle occurs from an electron transfer as a result of dissociation of coordinated hydroxyl ion to the iron atom in the photoexcited state, which may also involve the OH,Fe charge transfer transition around 360 nm. Copyright © 2001 John Wiley & Sons, Ltd. [source] Transformation of organic molecules on the low-valent {M(Ph2PCH2CH2PPh2)2} moiety derived from trans -[M(N2)2(Ph2PCH2CH2PPh2)2] or related complexes (M = MO, W)THE CHEMICAL RECORD, Issue 5 2001Hidetake Seino Abstract A zero-valent {M(Ph2PCH2CH2PPh2)2} moiety (M = Mo, W) generated in situ by dissociation of the N2 ligands in trans -[M(N2)2(Ph2PCH2CH2PPh2)2] can activate ,-accepting organic molecules including isocyanides and nitriles, which undergo the electrophilic attack caused by a strong ,-donation from a zero-valent metal center. Cleavage of a variety of C,X bonds (X = H, C, N, O, P, halogen) also occurs at their electron-rich sites through oxidative addition to form reactive intermediates, which subsequently degradate to yield smaller molecules either bound to or dissociated from the metal center. The mechanism is substantiated unambiguously by isolation of numerous intermediate stages. © 2001 John Wiley & Sons, Inc. and The Japan Chemical Journal Forum Chem Rec 1:349,361, 2001 [source] | |||||||||||||||||||||||||||||||