|
| ||
|
|
||
Bidentate Ligands (bidentate + ligand)
Selected AbstractsA Stable (Amino)(phosphino)carbene as Bidentate Ligand for Palladium and Nickel Complexes: Synthesis, Structure, and Catalytic Activity.CHEMINFORM, Issue 29 2006Emmanuelle Teuma 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] Norbornene Bidentate Ligands: Coordination Chemistry and Enantioselective Catalytic ApplicationsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 5 2010Fernando Fernández Abstract N - and P-donor derivatives have been prepared by functionalization of a readily available norbornene precursor. Palladium catalytic systems containing these new ligands were applied in allylic substitution, and yielded high activities and excellent enantioselectivities for the allylic alkylation and amination reactions (ee up to 97,%). A full coordination analysis of the catalytic precursors including modelling studies was also carried out. [source] Combinations of Acidic and Basic Monodentate Binaphtholic Phosphites as Supramolecular Bidentate Ligands for Enantioselective Rh-Catalyzed HydrogenationsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 15 2009Luca Pignataro Abstract A small library of chiral BINOL-derived monodentate phosphites containing either a carboxylic acid (-COOH, A1,A3) or a tertiary amine (-NMe2, B1,B4) was synthesized. The ligand combinations were screened in the enantioselective rhodium-catalyzed hydrogenation of methyl 2-acetamidoacrylate. The heterocombinations of the amine-derived phosphite (R)- B2 and of a carboxylic-phosphite [(R)- A1, (R)- A2, (R)- A3] displayed a slightly higher level of enantioselectivity compared to the corresponding homocombinations [up to 90,% ee using (R)- A1/(R)- B2]. The nature and extent of the interaction between the acidic and basic ligands in the rhodium complexes were studied by IR and 31P-NMR spectroscopy. The formation of an intramolecular salt in the Rh-heterocomplex, between the carboxylic acid and the tertiary amine, was suggested by the IR spectra. The selective formation of the Rh-heterocomplex was quantitatively assessed by 31P-NMR spectroscopy, using a modified acidic ligand (R)- A1-Me. In this way, a moderate (ca. 70:30) heterocomplex/homocomplexes ratio was determined.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Synthesis of "V-Shaped" syn -Bidentate Ligands Based on Mesitylene-Derived [1.1.1.1]Metacyclophane Blocked in a 1,3-Alternate ConformationEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 2 2003Cédric Klein Abstract A series of five new syn -bidentate ligands 14,18 based on the [1.1.1.1]metacyclophane backbone blocked in a 1,3-alternate conformation was achieved. The common building block for the preparation of ligands bearing two interaction sites located in a syn fashion (CN, SMe, p -pyridyl, p -methoxyphenyl and p -methylthiophenyl) is the dibromo derivative 12. All reported ligands were fully characterised by classical analytical methods and their 1,3-alternate conformation demonstrated. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Cover Picture: Bidentate Ligands by Self-Assembly through Hydrogen Bonding: A General Room Temperature/Ambient Pressure Regioselective Hydroformylation of Terminal Alkenes (Adv. Synth.ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-13 2005Catal. Abstract The cover picture shows a typical industrial reaction, hydroformylation of terminal alkenes, made possible in a test tube with ambient pressure and room temperature with high regioselectivities. For more details, see the Communication by Wolfgang Seiche, Alexander Schuschkowski, and Bernhard Breit on pages 1488,1494. [source] Synthesis of Novel Bisphosphine-Containing Polymers and Their Applications as Bidentate Ligands for Nickel(0)-Catalyzed Cross-Coupling Reactions.CHEMINFORM, Issue 37 2006Yong Lu 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] Self-Assembly of Bidentate Ligands for Combinatorial Homogeneous Catalysis: Asymmetric Rhodium-Catalyzed Hydrogenation.CHEMINFORM, Issue 31 2006Martine Weis 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] Chiral Phosphine,Olefin Bidentate Ligands in Asymmetric Catalysis: Rhodium-Catalyzed Asymmetric 1,4-Addition of Aryl Boronic Acids to Maleimides.CHEMINFORM, Issue 48 2005Ryo Shintani Abstract For Abstract see ChemInform Abstract in Full Text. [source] Three-Component Entanglements Consisting of Three Crescent-Shaped Bidentate Ligands Coordinated to an Octahedral Metal CentreCHEMISTRY - A EUROPEAN JOURNAL, Issue 31 2007Fabien Durola Abstract 3,3,-Biisoquinoline ligands (biiq) L, bearing aromatic substituents on their 8 and 8, positions, have been used to generate interwoven systems consisting of three crescent-shaped ligands disposed around an octahedral metal centre. Mono-ligand complexes of the type [ReL(CO)3py]+ (py: pyridine) have also been prepared, leading to sterically non-hindering complexes in spite of the endotopic nature of the chelate used. The three-component entanglements have been prepared by using either FeII or RuII as gathering metal centre. The synthetic procedure is simple and efficient, affording fully characterised complexes as their PF6 or SbCl6 salts. X-ray crystallography clearly shows that the crescent-shaped ligands do not repel each other in the tris-chelate complexes. In an analogous way, the ReI complexes show open structures with no steric repulsion between the L ligand and the ancillary CO or py groups. The FeL3 or RuL3 compounds are very unusual in the sense that, contrary to all the other tris-bidentate chelate complexes made till now, the three organic components are tangled up, in a situation which will be very favourable to the formation of new non trivial topologies of the catenane type. [source] Metal Effects on the Asymmetric Synthesis of a New Heterobidentate As/P=S LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2010Mengtao Ma Abstract The cycloaddition reaction between 3,4-dimethyl-1-phenylarsole and diphenylvinylphosphane sulfide was promoted by chiral palladium and platinum complexes containingortho -metalated (S)-[1-(dimethylamino)ethyl]naphthalene. They exhibited similar stereoselectivity; the palladium cycloadducts could not be separated via column chromatography and fractional crystallization, however, the corresponding platinum complexes could be successfully converted into their enantiomerically pure counterpart. A formal arsanylidene elimination reaction was observed on the liberated free As/P=S bidentate ligand. [source] New Coordination Modes of L -Ascorbic Acid and Dehydro- L -ascorbic Acid as Dianionic Chelating Ligand for PlatinumEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2008Paola Bergamini Abstract A variety of coordination modes of L -ascorbic acid as an anionic bidentate ligand has been exploited to prepare platinum(II) complexes 1,7 that contain phosphanes or R,R -dach (1R,2R -diaminocyclohexane) as neutral ligands in which O2, O3, O5, O6 and C2 act as anionic donating functionalities. An alternative synthetic route to known O2,O3 complexes is proposed, and their solubility in water has been enhanced by introducing PTA (1,3,5-triaza-7-phosphaadamantane) as a neutral ligand. A new coordination mode of ascorbic acid (O2 and O3 protected) as an O5,O6-diolate chelating ligand has been characterised in solution by NMR spectroscopy and in the solid state by X-ray crystallography. The first example of a platinum complex that contains dehydroascorbic acid, 7, has also been prepared and its X-ray crystal structure has been determined. The antiproliferative activity in vitro of complexes 1,7 has been tested, and the best values were obtained for the DHA complex 7, which was found to be more active than cisplatin on both a cisplatin-sensitive and a cisplatin-resistant cell line.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Syntheses and Crystal Structures of Tetrakis(arylamidine)nickel(II) Chloride and Bis[2,4-dipyridyl-1,3,5-triazapentadienato]nickel(II)EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2004Jianping Guo Abstract The reaction of LiN(SiMe3)2 with arylnitrile, followed by the addition of anhydrous NiCl2 gives ionic complexes of the general formula [Ni{H2NC(Ar)=NH}4]Cl2 (Ar = Ph 1, p -tolyl 2). When the above reaction is carried out with cyanopyridine instead of arylnitrile under the same reaction conditions, neutral complexes of the general formula [{HN=C(Py)N=C(Py)NH}2Ni] (Py = 4-pyridyl, 3; 3-pyridyl, 4] are obtained. Compound 1 undergoes a metathesis reaction with sodium benzoate to give the neutral complex [(PhCO2)2Ni {H2NC(Ph)=NH}4] (5). Magnetic susceptibility measurements show that 1,4 are diamagnetic and that 5 is paramagnetic with two unpaired electrons. These results suggest that 1,4 are d8 square-planar complexes and 5 is an octahedral complex. The solid state structures of compounds 1,5 were determined by X-ray crystallography. Structural analyses reveal that 1 and 2 form a one-dimensional network through charge-assisted hydrogen bonds; whereas 5 forms a one-dimensional network through hydrogen bonds only. In complexes 3 and 4, the 2,4-dipyridyl-1,3,5-triazapentadienyl ligand behaves as a bidentate ligand forming a six-membered ring with the metal ion. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Novel results obtained by freezing berry pseudorotation of phosphoranes (10-P-5)HETEROATOM CHEMISTRY, Issue 5 2002Kin-ya Akiba By freezing Berry pseudorotation of spirophosphoranes with recourse to the rigidity of the Martin bidentate ligand, we successfully prepared configurationally stable enantiomeric pairs of optically active phosphoranes, and could isolate "anti-apicophilic" C-apical O-equatorial (O-cis) phosphoranes. The effect of ,*PO orbital of the O-cis phosphorane was investigated both experimentally and theoretically. O-cis phosphoranes were revealed to be much more electrophilic at the phosphorus atom than O-trans isomers by experimental studies. The acidity of the ,-proton of an O-cis benzylphosphorane was found to be higher than that of the corresponding O-trans isomer. By the reaction of the ,-carbanion of an O-cis benzylphosphorane with PhCHO, we succeeded in the first isolation and full structural characterization of a 12-P-6 phosphate bearing an oxaphosphetane ring, the intermediate in the Wittig type reaction using a 10-P-5 phosphorane. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:390,396, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10072 [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] Intermolecular C,H..., interactions in 1,5-diphenyl-3-(2-pyridyl)-2-pyrazolineACTA CRYSTALLOGRAPHICA SECTION C, Issue 6 2010Miquel Barceló-Oliver The title compound, C20H17N3, is a derivative of 1,3,5-triaryl-2-pyrazoline and can act as an N,N,-bidentate ligand. This molecule features strong fluorescence that can be explained by an extended pyridyl,C=N,N,phenyl system. The three-dimensional structure is formed by means of an extended network of weak C,H..., hydrogen bonds supported by ,,, interactions. [source] Powder study of poly[(,2 -2,2-dimethylpropane-1,3-diyl diisocyanide)-,2 -iodido-silver(I)]ACTA CRYSTALLOGRAPHICA SECTION C, Issue 3 2009Mwaffak Rukiah In order to explore the chemistry of the bidentate ligand 2,2-dimethylpropane-1,3-diyl diisocyanide and to investigate the effect of counter-ions on the polymeric structure of (2,2-dimethylpropane-1,3-diyl diisocyanide)silver(I) complexes, the title polymeric compound, [AgI(C7H10N2)]n, was synthesized by treatment of 2,2-dimethylpropane-1,3-diyl diisocyanide with AgI. X-ray powder diffraction studies show, as expected, a polymeric structure, similar to the very recently reported Cl, and NO3, analogues [AgX(C7H10N2)]n (X = Cl, or NO3,). In the title structure, the AgI centre is bridged to two adjacent AgI neighbours by bidentate 2,2-dimethylpropane-1,3-diyl diisocyanide ligands via the NC groups to form [Ag{CNCH2C(CH3)2CH2NC}]n chains. The iodide counter-ions crosslink the AgI centres of the chains to form a two-dimensional polymeric {[Ag{CNCH2C(CH3)2CH2NC}]I}n network. This study also shows that this bidentate ligand forms similar polymeric structures on treatment with AgX, regardless of the nature of the counter-ion X,, and also has a strong tendency to form polymeric complexes rather than dimeric or trimeric ones. [source] A novel two-dimensional zinc(II) coordination polymer with 6-mercaptonicotinic acidACTA CRYSTALLOGRAPHICA SECTION C, Issue 1 2008Yong Wang The novel title ZnII coordination polymer, poly[bis(,-6-thioxo-1,6-dihydropyridine-3-carboxylato-,2S:O)zinc(II)], [Zn(C6H4NO2S)2]n, consists of two crystallographically independent zinc centers and two 6-mercaptonicotinate (Hmna,) ligands. Each ZnII atom is four-coordinated and lies at the center of a distorted tetrahedral ZnS2O2 coordination polyhedron, bridged by four Hmna, ligands to form a two-dimensional (4,4)-network. Each Hmna, ion acts as a bridging bidentate ligand, coordinating to two ZnII atoms through the S atom and a carboxyl O atom. The metal centers reside on twofold rotation axes. The coordination mode of the S atoms and N,H...O hydrogen-bonding interactions between the protonated N atoms and the uncoordinated carboxyl O atoms give the extended structure a wavelike form. [source] Polymer Complexes: supramolecular assemblies and structures of poly[N -(2,-pyridyl)propenamide] complexesAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 5 2004A. T. A. Mubarak Abstract A number of new polymer complexes of palladium(II), platinum(II) and copper(II) containing homopolymer (N -(2,-pyridyl)propenamide; APH) and various anions (Cl,, Br,, I, or NO3,) have been synthesized and characterized by elemental analyses, magnetic susceptibility, electron paramagnetic resonance, IR and reflectance spectral measurements. The homopolymer shows three types of coordination behavior. In the mononuclear polymer complexes 1,6 and 9 it acts as a neutral bidentate ligand chelated through the pyridine-nitrogen and amide-oxygen atoms, whereas in the square-planar [Pd(APH)2X2] (X = Cl, Br) unidentate APH is coordinated through the pyridine-nitrogen atom alone. Under alkaline conditions APH is deprotonated in the presence of palladium(II) to form [Pd(AP)2] (10), AP being an anionic bidentate ligand and chelating through the pyridine-nitrogen and amide-oxygen atoms. The poly-chelates are of 1:1 and 1:3 (metal:homopolymer) stoichiometry and exhibit six-coordination. The polymer complexes of stoichiometric [(APH)2CuX2] contain square planar (APH)2 Cu2+ units and the anions X, are in the axial positions, giving distorted octahedral configurations. From the electron paramagnetic resonance and spectral data, the orbital reduction factors were calculated. Copyright © 2004 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] Bis(azido-,N)[(6R,7S,8S,14S)-(,)-sparteine-,2N,N,]copper(II)ACTA CRYSTALLOGRAPHICA SECTION C, Issue 2 2003Yong-Kyu Kim In the title compound, [Cu(N3)2(C15H26N2)], the chiral alkaloid (,)- l -sparteine (Sp) acts as a bidentate ligand, with two azide ligands occupying the remaining coordination sites, forming a distorted CuN4 tetrahedron. The dihedral angle between the NSp,Cu,NSp and Nazide,Cu,Nazide planes is 55.3,(2)°. Principal dimensions include Cu,NSp,=,2.011,(6) and 2.025,(5),Ĺ, and Cu,Nazide,=,1.939,(6) and 1.934,(7),Ĺ. The mid-point of the NSp,NSp line does not lie exactly in the Nazide,Cu,Nazide plane, but is tilted towards one of the NSp atoms by 0.026,Ĺ. [source] Hydroxycinnamic Acids as DNA-Cleaving Agents in the Presence of CuII Ions: Mechanism, Structure,Activity Relationship, and Biological ImplicationsCHEMISTRY - A EUROPEAN JOURNAL, Issue 46 2009Gui-Juan Fan Abstract The effectiveness of hydroxycinnamic acids (HCAs), that is, caffeic acid (CaA), chlorogenic acid (ChA), sinapic acid (SA), ferulic acid (FA), 3-hydroxycinnamic acid (3-HCA), and 4-hydroxycinnamic acid (4-HCA), as pBR322 plasmid DNA-cleaving agents in the presence of CuII ions was investigated. Compounds bearing o -hydroxy or 3,5-dimethoxy groups on phenolic rings (CaA, SA, and ChA) were remarkably more effective at causing DNA damage than the compounds bearing no such groups; furthermore, CaA was the most active among the HCAs examined. The involvement of reactive oxygen species (ROS) and CuI ions in the DNA damage was affirmed by the inhibition of the DNA breakage by using specific scavengers of ROS and a CuI chelator. The interaction between CaA and CuII ions and the influence of ethylenediaminetetraacetic acid (EDTA), the solvent, and pH value on the interaction were also studied to help elucidate the detailed prooxidant mechanism by using UV/Vis spectroscopic analysis. On the basis of these observations, it is proposed that it is the CaA phenolate anion, instead of the parent molecule, that chelates with the CuII ion as a bidentate ligand, hence facilitating the intramolecular electron transfer to form the corresponding CaA semiquinone radical intermediate. The latter undergoes a second electron transfer with oxygen to form the corresponding o -quinone and a superoxide, which play a pivotal role in the DNA damage. The intermediacy of the semiquinone radical was supported by isolation of its dimer from the CuII -mediated oxidation products. Intriguingly, CaA was also the most cytotoxic compound among the HCAs toward human promyelocytic leukemia (HL-60) cell proliferation. Addition of exogenous CuII ions resulted in an effect dichotomy on cell viability depending on the concentration of CaA; that is, low concentrations of CaA enhanced the cell viability and, conversely, high concentrations of CaA almost completely inhibited the cell proliferation. On the other hand, when superoxide dismutase was added before, the two stimulation effects of exogenous CuII ions were significantly ameliorated, thus clearly indicating that the oxidative-stress level regulates cell proliferation and death. These findings provide direct evidence for the antioxidant/prooxidant mechanism of cancer chemoprevention. [source] Comparative Experimental and EXAFS Studies in the Mizoroki,Heck Reaction with Heteroatom-Functionalised N-Heterocyclic Carbene Palladium CatalystsCHEMISTRY - A EUROPEAN JOURNAL, Issue 13 2007Steven G. Fiddy Dr. Abstract A study on the Mizoroki,Heck coupling of selected aryl bromides with acrylates catalysed by a series of Pd complexes of bidentate pyridyl-, picolyl-, diphenylphosphinoethyl- and diphenylphosphinomethyl-functionalised N-heterocyclic carbene (NHC) is reported. The observed activity is dependent on the type of solvent and base used and the nature of the "classical" donors of the mixed-donor bidentate ligand and its bite angle. A mechanistic model is presented for the pyridine-functionalised NHC complexes based on an in situ EXAFS study under dilute catalyst conditions (2,mM Pd). The model involves pre-dissociation of the pyridine functionality and oxidative addition of ArBr in the early stages of the reaction, as well as formation of monomeric and dimeric Pd species at the time of substrate conversion. [source] Analysis of Single-Molecule Fluorescence Spectroscopic Data with a Markov-Modulated Poisson ProcessCHEMPHYSCHEM, Issue 14 2009Mark Jäger Dr. Abstract We present a photon-by-photon analysis framework for the evaluation of data from single-molecule fluorescence spectroscopy (SMFS) experiments using a Markov-modulated Poisson process (MMPP). A MMPP combines a discrete (and hidden) Markov process with an additional Poisson process reflecting the observation of individual photons. The algorithmic framework is used to automatically analyze the dynamics of the complex formation and dissociation of Cu2+ ions with the bidentate ligand 2,2,-bipyridine-4,4,dicarboxylic acid in aqueous media. The process of association and dissociation of Cu2+ ions is monitored with SMFS. The dcbpy-DNA conjugate can exist in two or more distinct states which influence the photon emission rates. The advantage of a photon-by-photon analysis is that no information is lost in preprocessing steps. Different model complexities are investigated in order to best describe the recorded data and to determine transition rates on a photon-by-photon basis. The main strength of the method is that it allows to detect intermittent phenomena which are masked by binning and that are difficult to find using correlation techniques when they are short-lived. [source] Better Performance of Monodentate P -Stereogenic Phosphanes Compared to Bidentate Analogues in Pd-Catalyzed Asymmetric Allylic AlkylationsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 21 2010Arnald Grabulosa Abstract The cationic allylpalladium complexes 3a,3f, 4a, 4e, 5e of type [Pd(,3 -2-Me-C3H4)P2]PF6 were synthesized using a group of monodentate P -stereogenic phosphanes, P=PPhRR, (a,f) and diphosphanes (PhRPCH2)2 (1a, 1e) or PhRPCH2Si(Me)2CH2PPhR (2e). The analogous cationic complexes with the disubstituted allyl group (,3 -1,3-Ph2 -C3H3) and monodentate phosphanes were not isolated as stable solids; only [PdCl(,3 -1,3-Ph2 -C3H3)P] (6a, 6d) were obtained. Palladium allyl complexes were screened as precatalysts in the allylic substitution of rac -3-acetoxy-1,3-diphenyl-1-propene (I) and (E)-3-acetoxy-1-phenyl-1-propene (III) with dimethyl malonate as the nucleophile. The various catalytic precursors showed a wide range of activity and selectivity. The bismonodentate phosphane complexes 3 are more active than the bidentate analogues. With regard to the regioselectivity, precursors containing monodentate phosphanes favour the formation of the linear product in the allylic substitution of cinnamyl acetate (III) compared with those containing bidentate phosphanes. With substrate I, compounds with the diphosphanes 1a and 1e, containing a five-membered chelate ring, gave low enantioselectivities (less than 10,% ee), but those with the diphosphane 2e, forming a six-membered chelate ring or with two monodentate phosphanes, afforded products with moderate enantioselectivity under standard conditions (ee up to 74,%). The results show that the performance of precursors containing monodentate phosphanes was superior to those containing bidentate ligands in both activity and selectivity. [source] Studies in Solution and the Solid State of Coordination Compounds Derived from LiBH4, NaBH4, and Bidentate Aromatic AminesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2010Milagros Aguilar-Martínez Abstract The mixture of 2,2,-bipyridylamine, 2,2,-bipyridine, 1,10-phenanthroline, 1,2-phenylendiamine, and 1,4-phenylendiamine each with LiBH4 and NaBH4 in a 1:1 molar ratio in THF yields seven new complexes of the type MBH4·L-THF and one complex of the type MBH4·L. These compounds were characterized by IR and NMR spectroscopy and X-ray single-crystal structure determinations. In the solid state, the [BH4], group is bidentate, as deduced from the stretching patterns observed in IR spectra and confirmed by X-ray single-crystal structure analysis. NMR spectroscopy showed that all amines act as bidentate ligands and are symmetrically coordinated to the metal cation. Complexes LiBH4 -2,2,-bipyridine-THF (1), NaBH4 -2,2,-bipyridine-THF (2), LiBH4 -1,10-phenanthroline-THF (3), and NaBH4 -1,10-phenanthroline-THF (4) have a discrete molecular structure, whereas the complexes LiBH4 -1,2-phenylendiamine-THF (5), NaBH4 -1,2-phenylendiamine-THF (6), LiBH4 -2,2,-dipyridilamine (7), and LiBH4 -1,4-phenylendiamine-THF (8) have polymeric structures in the solid state. N -borane-dipyridylamine adduct 9 was isolated from an aged solution of 7. IR spectroscopy of the new complexes showed that the structures of complexes 1, 3, 4, and 6 are maintained in the solid state and in solution. A rotational barrier for the [BH4], group of less than 38 KJ,mol,1 was estimated for some of the new complexes. [source] Molybdenum Carbonyl Complexes Bearing PN Ligands Based on 2-Aminopyridine,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 27 2009Christina Maria Standfest-Hauser Abstract Molybdenum complexes of the general formula Mo(PN)(CO)4 containing both achiral and chiral phosphorus-nitrogen donor bidentate ligands based on 2-aminopyridine were prepared and characterized by their NMR and IR spectra. The oxidative addition of allyl bromide to Mo(PN)(CO)4 was studied with PN = N -(diisopropylphosphanyl)-2-aminopyridine (PN- iPr). X-ray structures of representative compounds were determined. The mechanism of the oxidative addition of allyl bromide to Mo(PN- iPr)(CO)4 was analyzed by DFT/B3LYP calculations. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] A Simple Building-Block Route to (Phosphanyl-carbene)palladium Complexes via Intermolecular Addition of Functionalised Phosphanes to IsocyanidesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 10 2009Michael R. Eberhard Abstract We present a straightforward protocol for making (phosphanyl-carbene)PdII complexes. These complexes have bidentate ligands containing an acyclic diamino- or aminooxy-carbene and a phosphane. The synthesis gives good yields (typically 70,90,%) for a variety of complexes (22 compounds). Moreover, it does not require the synthesis of imidazolium salts nor the a priori generation of free carbenes. Three of the new complexes were tested as catalysts for Sonogashira and Hay coupling reactions, with good yields and selectivities. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] A Theoretical Study on the Reactivity of a Rhenium Hydroxo-Carbonyl Complex Towards ,-LactamsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 29 2008Violeta Yeguas Abstract The mechanism of the reaction between the complex [Re(OH)(CO)3(N2C2H4)] and azetidin-2-one or 3-formylamino- N -sulfonatoazetidin-2-one was investigated by using the B3LYP density functional theory methodology in conjunction with the PCM-UAHF model to take into account solvent effects. According to our calculations, the rate-determining energy barrier for the azetidin-2-one case of 38.8 kcal,mol,1, becomes 25.7 kcal,mol,1 in the case of the 3-formylamino- N -sulfonatoazetidin-2-one species. The presence of the sulfonato group is crucial for the cleavage of the ,-lactam N1,C2 bond by the Re complex thanks to the interaction of the sulfonato group with the hydroxy and bidentate ligands of the complex. This could be of interest for the synthesis of ,-amino acids and their derivatives from ,-lactams under mild conditions and in solvents of low polarity promoted by organometallic complexes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Tetranuclear Nickel Complexes Composed of Pairs of Dinuclear LNi2 Fragments Linked by 4,4,-Bipyrazolyl, 1,4-Bis(4,-pyrazolyl)benzene, and 4,4,-Bipyridazine: Synthesis, Structures, and Magnetic PropertiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 20 2007Vasile Lozan Abstract The ability of the ligands 4,4,-bipyrazolyl (H2bpz), 1,4-bis(4,-pyrazolyl)benzene (H2bpzb), and 4,4,-bipyridazine (bpdz) to link two dioctahedral LNi2 units has been examined. Thefollowing complexes were prepared: [L1NiII2(Hbpz)][BPh4] (6[BPh4]), [L1NiII2(bpdz)][ClO4]2 (7[ClO4]2), [(L1NiII2)2(bpzb)][BPh4]2 (8[BPh4]2), and [(L2NiII2)2(bpz)][BPh4]2 (9[BPh4]2), where (L1)2, and (L2)2, represent macrocyclic hexaaza-dithiophenolate ligands. All complexes have been characterised by UV/Vis spectroscopy, IR spectroscopy, and X-ray crystallography. Whereas (Hbpz), and bpdz in 6[BPh4]2 and 7[ClO4]2 act as bidentate ligands coordinating to only one [LNi2]2+ unit, in 8[BPh4]2 and 9[BPh4]2 the (bpzb)2, and(bpz)2, units are tetradentate linkers. This is qualitatively explained in terms of the absence or presence of steric repulsions between the tBu groups of the supporting ligands and the length of the coligands. The structures of the tetranuclear complexes differ mainly in the distance between the center of the Ni···Ni axes of the isostructural [LNi2] units {14.040(1) Ĺ in 8[BPh4]2, 9.184(1) Ĺ in 9[BPh4]2}. The two Ni2pyrazolato planes in 9[BPh4]2 are coplanar. An analysis of the temperature-dependent magnetic susceptibility data for 9[BPh4]2 reveals the presence of weak ferromagnetic exchange interactions between the NiII ions in the binuclear [L2Ni2] subunits with values for the magnetic exchange constant J1 of 23.97 cm,1 (H = ,2JS1S2). The exchange coupling across the dipyrazolato bridge is less than 0.1 cm,1, suggesting that no significant interdimer exchange coupling occurs in 9[BPh4]2. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Bis(fluoromesityl) Palladium Complexes, Archetypes of Steric Crowding and Axial Protection by ortho Effect , Evidence for Dissociative Substitution Processes , Observation of 19F,19F Through-Space CouplingsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 11 2004Camino Bartolomé Abstract Bisarylated complexes trans -[Pd(Fmes)2(SR2)2] [Fmes = 2,4,6-tris(trifluoromethyl)phenyl (fluoromesityl); SR2 = SMe2, tht; tht = tetrahydrothiophene] are precursors for various bisarylated fluoromesityl palladium(II) complexes by ligand-substitution reactions. Boiling under reflux in acetonitrile gives the mixed complexes trans -[Pd(Fmes)2(NCMe)(SR2)], whereas boiling under reflux in toluene leads to trans -[PdCl2L2] (L = PMe3, tBuNC, pTol-NC, 4-MePy), in the presence of neutral monodentate ligands, or to (NnBu4)[trans -Pd(Fmes)2I(SR2)] when treated with (NnBu4)I. trans -[Pd(Fmes)2(SMe2)2] reacts with bidentate ligands, also boiling under reflux in toluene, to give [Pd(Fmes)2(L,L)] [L,L = Me2bipy, 2,2, - biquinolyl, ,2N,N, -OCPy2, dppm (Ph2PCH2PPh2), dppe (Ph2PCH2CH2PPh2), pte (PhSCH2CH2SPh), ,2S,N -SPPh2Py, ,2O,N -OPPhPy2], or the bimetallic complex [Pd(Fmes)2(,-1,N:1,2,O:2,N -Py2MeCO)Pd(Fmes)(SMe2)] (characterized by X-ray diffractometry) when treated with (OH)(CH3)CPy2. The crowding associated with two Fmes groups produces several interesting features: (1) trans complexes are preferred over cis complexes, against the expected electronic preferences; (2) the low-temperature NMR spectra of several complexes, or the X-ray diffraction structure of [Pd(Fmes)2(2,2, - biquinolyl)], reveal significant structural distortions associated with steric crowding; (3) the need for boiling under reflux in the synthesis suggests a dissociative substitution mechanism, which is unknown so far for Pd; (4) some of the complexes show 19F,19F through-space couplings. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] | |||||||||||||||||||||||||