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Ligands
Kinds of Ligands Terms modified by Ligands Selected AbstractsSynthesis of Polystyrene- block -Poly(methyl methacrylate) with Fluorene at the Junction: Sequential Anionic and Controlled Radical Polymerization from a Single CarbonMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 24 2009Nathan D. Contrella Abstract Polystyrene- block -poly(methyl methacrylate) (PS- b -PMMA) has been synthesized by sequential anionic and reverse atom transfer radical polymerization (ATRP) or a variation of nitroxide mediated polymerization (NMP) from a single initiating site, specifically the 9-carbon on 2,7-dibromofluorene or fluorene. The addition of the second arm (PS) relied on thermal decomposition of 2,2,-azoisobutyronitrile (AIBN) to generate radicals, abstracting the 9-H on the polymer-bound fluorene species to form the initiating radical. Styrene was not present in the reaction mixture when AIBN was decomposed, preventing competition between addition across the monomeric alkene and hydrogen abstraction from the fluorene. After 1,h, styrene was introduced and mediation of the subsequent radical polymerization was achieved by the presence of CuCl2/ligand or TEMPO. Characterization of the diblock copolymers by gel permeation chromatography (GPC) revealed substantial shifts in number average molecular weight () values compared to the anionically prepared PMMA macroinitiator, while polydispersity indices (PDI's) remained relatively low (typically,<,1.5). Characterization by UV detection with GPC (at 310,nm) verified that the diblock polymer is chromophore-bound, which was further verified by UV-vis spectroscopy of the isolated diblock. [source] Application of a Carbon Paste Electrode Modified with a Schiff Base Ligand to Mercury Speciation in WaterELECTROANALYSIS, Issue 11 2005Montserrat Colilla Abstract A carbon paste electrode, modified with benzylbisthiosemicarbazone is used for mercury speciation in water samples. Mercury ion is selectively accumulated on the electrode surface at open circuit and its analysis was performed by cyclic voltammetry or square-wave voltammetry (SWV). A detection limit of 8,,g L,1 (3,) was found for 15,min of accumulation using SWV as measurement technique. The effect of several metallic ions and organic substances on voltammetric signal is examined. For speciation purposes, a ligand competition methodology between ligands in solution and electrode is used. Model mercury complexes are characterized as a function of their dissociation kinetics. The method was applied to mercury speciation in water samples from the Jarama River in Madrid. [source] Linear Coinage Metal Complexes Stabilized by a Group 13 Metalloid LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 28 2010Ganesan Prabusankar Abstract The synthesis and structural characterization of the linear, cationic complex [{(DDP)Ga}2Cu][OTf]·2C6H5F (2, Tf = O2SCF3) stabilized by the monodentate, gallium-based ligand Ga(DDP) (DDP = [HC{(CMe)N(2,6- iPr2C6H3)}2],), as well as NMR spectroscopic evidence for the formation of the corresponding silver compound [{(DDP)Ga}2Ag][Al(hfip)4] (3, hfip = [OC(H)(CF3)2]), are reported. The remarkable steric properties of this gallium-based ligand permit the stabilization of 2, which exhibits an unusual linear geometry and a coordination number of two. [source] [FeFe]-Hydrogenase Models: Overpotential Control for Electrocatalytic H2 Production by Tuning of the Ligand ,-Acceptor AbilityEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 25 2010Fengwei Huo Abstract In the search for synthetic competitive catalysts that function with hydrogenase-like capability, a series of (Pyrrol-1-yl)phosphane-substituted diiron complexes [(,-pdt)Fe2(CO)5L] [pdt = propanedithiolate, L = Ph2PPyr (2), PPyr3 (4); Pyr = pyrrolyl] and [(,-pdt)Fe2(CO)4L2] [L = Ph2PPyr (3), PPyr3 (5)] were prepared as functional models for the active site of Fe-only hydrogenase. The structures of these complexes were fully characterized by spectroscopy and X-ray crystallography. In the IR spectra the CO bands for complexes 2,5 are shifted to higher energy relative to those of complexes with "traditional" phosphane ligands, such as PPh3, PMe3, and PTA (1,3,5-triaza-7-phosphaadamantane), indicating that (pyrrol-1-yl)phosphanes are poor ,-donors and better ,-acceptors. The electrochemical properties of complexes 2,5 were studied by cyclic voltammetry in CH3CN in the absence and presence of the the weak acid HOAc. The reduction potentials of these complexes show an anodic shift relative to other phosphane-substituted derivatives. All of the complexes can catalyze proton reduction from HOAc to H2 in CH3CN at their respective FeIFe0 level. Complex 4 is the most effective electrocatalyst, which catalytically generates H2 from HOAc at ,1.66 V vs. Fc+/Fc with only ca. 0.2 V overpotential in CH3CN. [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] A ,3 -Alkoxo-Bridged Tetranuclear [Cu4L2] Copper(II) Complex of a Hexadentate N2O4 Donor Ligand with a [6 + 0] Cu4O4 Cubane Core: Synthesis, Crystal Structure, and Magnetic PropertiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2010Dipankar Maity Abstract A novel hexacoordinating non-Schiff base ligand (H4L) with N2O4 donor atoms has been synthesized by simple Mannich reactions. The use of this ligand with Cu(ClO4)2·6H2O in different molar ratios as well as pH leads to the formation of a mononuclear species and a tetranuclear CuII complex possessing a cubane [Cu4L2] core with almost equal Cu···Cu separation. In the presence of an excess amount of copper(II) ions and triethylamine at reflux, the mononuclear [CuH2L] species can be converted into the tetranuclear one, whereas the reverse process was not observed even after prolonged reaction time. Both the complexes have been characterized by single-crystal X-ray diffraction and magnetic measurements. Magnetic studies reveal that complex 1 displays a paramagnetic Curie-type behavior whereas 2 displays a singlet-spin ground state induced by strong intramolecular antiferromagnetic interactions. [source] Syntheses, Structures and Magnetic Properties of Trinuclear CuIIMIICuII (M = Cu, Ni, Co and Fe) and Tetranuclear [2×1+1×2] CuIIMnII,2CuII Complexes Derived from a Compartmental Ligand: The Schiff Base 3-Methoxysalicylaldehyde Diamine Can also Stabilize a CocrystalEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 20 2010Arpita Biswas Abstract The present investigation describes syntheses, characterization and studies of the mononuclear compound [CuIIL,(H2O)] (1), the triangular, trinuclear monophenoxido-bridged compounds [{CuIIL}2MII(H2O)2](ClO4)2·nH2O [2 (M = Cu, n = 0), 3 (M = Ni, n = 3), 4 (M = Co, n = 0), 5 (M = Fe, n = 0)] and the tetrametallic self-assembled complex [{CuIILMnII(H2O)3}{CuIIL}2](ClO4)2·H2O (6) derived from compartmental Schiff base ligand, H2L, which is the [2+1] condensation product of 3-methoxysalicylaldehyde and trans -1,2-diaminocyclohexane. Single-crystal X-ray structures of 2, 5 and 6 were determined. Two pairs of terminal···central metal ions in the trinuclear cores in 2 and 5 are monophenoxido-bridged. Interestingly, the CuO6 and FeO6 environments have tetragonally compressed octahedral geometries. On the other hand, the structure of 6 reveals that it is a [2×1+1×2] cocrystal of one diphenoxido-bridged dinuclear [CuIILMnII(H2O)3]2+ dication and two mononuclear [CuIIL] moieties. Cocrystallization in 6 takes place as a result of water encapsulation. The variable-temperature (2,300 K) magnetic susceptibilities of compounds 2,6 have been measured. The exchange integrals obtained are: the CuII3 compound 2, J = ,78.9 cm,1; the CuIINiIICuII compound 3, J = ,22.8 cm,1; the CuIICoIICuII compound 4, J = ,7.8 cm,1; the CuIIFeIICuII compound 5, J = ,3.0 cm,1; the CuII3MnII compound 6, J = ,15.1 cm,1. The monophenoxido-bridging core in 3 and 4 has been proposed after comparison of the structures and magnetic properties of these two compounds with those of 2, 5 and related other compounds. This paper presents rare examples of monophenoxido-bridged CuIIMIICuII (M = Cu, Ni, Co and Fe) compounds, provides an understanding of the structures from magnetic exchange integrals, and, most importantly, reports on the first example of a cocrystal derived from a 3-methoxysalicylaldehyde diamine compartmental ligand. [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] Mono- and Binuclear Arylnickel Complexes of the ,-Diimine Bridging Ligand 2,2,-Bipyrimidine (bpym)EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 6 2010Axel Klein Abstract The mono- and binuclear organometallic NiII complexes [(,-bpym){Ni(Mes)Br}n] (bpym = 2,2,-bipyrimidine; n = 1 or 2; Mes = mesityl = 2,4,6-trimethylphenyl) were prepared and characterised electrochemically and spectroscopically (NMR, UV/Vis/NIR) in detail. The long-wavelength absorptions for the binuclear complex reveal a marked electronic coupling of the two metal centres over the ligand bridge via their low-lying ,*-orbitals. While the mononuclear complex undergoes rapid dissociation of the bromido ligand after one-electron reduction the binuclear derivative exhibits reversible reductive electrochemistry and both of them yield stable radical anionic complexes with mainly bpym ligand centred spin density as shown by EPR spectroscopy of the free ligand bpym and the nickel complexes. The molecular structure of the binuclear bpym complex [(,-bpym){Ni(Mes)Br}2] was studied by EXAFS in comparison to the mononuclear analogue [(bpym)Ni(Mes)Br] revealing markedly increased Ni,C/N distance of the first coordination shell for the binuclear derivative suggesting an optimum overlap for the mononuclear complex, while two nickel complex fragments {Ni(Mes)Br} are seemingly too large to fit into the bis-chelate coordination site. [source] Salen Ligands Revisited: Synthesis and Application of a Planar Chiral "Ferro-Salen" LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 5 2010Jochen Niemeyer Abstract Condensation of the O-protected planar chiral hydroxyferrocene carbaldehyde (Sp)- 1 with ethylenediamine, followed by deprotection gave rise to the "ferro-salen" ligand (Sp,Sp)- 3 in good yield. This scaffold was used for the preparation of a series of metal complexes [(Sp,Sp)- 4/5/6], which were subsequently applied for the Lewis acid catalyzed asymmetric trimethylsilylcyanation of benzaldehyde. [source] Single End-to-End Azidocopper(II) Chain Based on an Electroactive Ligand: A Structural, Electrochemical, Magnetic and Ab Initio StudyEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 31 2009Guillaume Pilet Abstract By combining azide and the (Z)-1,1,1-trifluoro-4-(quinolin-8-ylamino)but-3-en-2-one enaminone ligand, HL, an azido-bridged copper(II) one dimensional polymer was synthesized in a one-pot reaction. The solved and refined crystal structure evidenced the unusual single and asymmetric end-to-end coordination mode of the azide ion. The redox properties of this complex were studied by cyclic voltammetry, andoxidation of the azido bridge was evidenced. Magneticmeasurements, combined with magnetostructural-driven analysis revealed a weak ferromagnetic interaction between the copper(II) ions within the N3, -bridged chains, complemented by an antiferromagnetic interaction between the chains mediated by ,,, interactions. A survey of the scarce literature of single end-to-end azido bridges, associated with quantum chemical ab initio calculations, was carried out to tentatively identify the relevant parameters driving the weak intrachain exchange interaction.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] A Dinuclear Double-Stranded Oxido Complex of ReV with a Bis(benzene- o -dithiolato) LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 27 2009Jorge S. Gancheff Abstract The reaction of [ReOCl3(PPh3)2] with 1,2-bis(2,3-dimercaptobenzamido)ethane (H4 - 1) in the presence of Na2CO3 in methanol under anaerobic conditions affords the dinuclear ReV oxido complex [PPh4]2[ReO(1)]2 containing two distorted square-pyramidal {ReVOS4} units bridged by the ligand strands in a double-stranded fashion. The coordinationgeometry around the metal centers is similar to the one observed for [ReO(bdt)2],. The ReS4 planes are arranged in a coplanar fashion and are not twisted around the metal,metal vector, which prevents the complex to adopt a helical structure. Luminescence studies show the presence of emission bands, which are assigned to singlet-singlet transitions exhibiting very fast decays (ca. 10 ns). Theoretical Density Functional (DFT) studies on geometry and electronic properties were performed employing the hybrid B3LYP and PBE1PBE functionals. While the general trends observed in the experimental data are well reproduced in all cases, a good agreement was obtained using PBE1PBE, in particular for the Re,S bonds. Natural Bond Orbitals (NBO) analysis indicates the presence of polarized Re,O and Re,S bonds, both of them polarized toward the non-metal. The calculation show that the molecular orbitals of the ReV are doubly degenerated, the occupied 5d orbital of rhenium lying beneath occupied sulfur-based MOs due to the rigid geometry imposed by the C,C backbone of the bis(benzene- o -dithiolato) ligands. The origin of all absorption bands is ascribed to a ligand-to-metal charge transfer (LMCT), in which occupied sulfur-based orbitals and unoccupied rhenium-centered orbitals are involved.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Monomeric and Dimeric Copper(II) Complexes of a Pyrrole-Containing Tridentate Schiff-Base LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2009Rongqing Li Abstract Three copper(II) complexes of (L1),, [CuL1Cl] (1), [CuL1Br]n (2) and [Cu2(L1)2(,1,3 -NCS)2] (3), and two copper(II) complexes of HL1, [Cu(HL1)X2] (X = Cl,, 4; X = Br,, 5), have been prepared and characterised [where HL1 is the Schiff-base ligand derived from pyrrole-2-carbaldehyde and 2-aminomethylpyridine]. The removal of a chloride ion and deprotonation of [Cu(HL1)Cl2] (4) to form [CuL1Cl] (1) worked well. However, attempts to protonate [CuL1Cl] with HCl to re-form [Cu(HL1)Cl2] were not successful. X-ray structure determinations revealed that 1 is a N3Cl-coordinated square-planar copper(II) monomer [CuL1Cl], whereas 3 is a doubly end-to-end thiocyanate-bridged square-pyramidal copper(II) dimer [Cu2(L1)2(,1,3 -NCS)2]. The structure determinations on 4 and 5 showed that in both cases the copper(II) ion is in a distorted square-planar N2X2 environment, with the pyrrole NH remaining non-deprotonated and uncoordinated. Variable-temperature magnetic susceptibility investigations carried out on the end-to-end thiocyanate doubly bridged square-pyramidal copper(II) dimer 3 showed that no magnetic coupling occurs between the two copper(II) ions; it exhibits Curie-like magnetic behaviour.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Solid-State and Solution Structure of Lanthanide(III) Complexes with a Flexible Py-N6 Macrocyclic LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2009Cristina Núñez Abstract Lanthanide complexes of a hexaaza macrocyclic ligand containing a pyridine head unit (L) were synthesized (Ln = La,Lu, except Pm). The solid-state structures of the corresponding La, Ce, Pr, Nd, and Lu complexes were determined by single-crystal X-ray crystallography, and they reveal the presence of three different mononuclear complexes with three different conformations of the macrocycle and coordination environments around the metal ions. In all complexes the lanthanide ion is coordinated in an endomacrocyclic manner to the six nitrogen donor atoms of the ligand. In the La, Ce, and Pr complexes the metal ions show a 12-coordinate mononuclear environment in which 3 nitrate anions coordinate in a bidentate fashion. However, in the Nd analogue the metal ion displays a 10-coordinated environment with the coordination of 2 bidentate nitrate groups, whereas Lu shows a 9-coordinate environment interacting with 2 nitrate ligands, one of them acting as bidentate and the second one coordinating in a monodentate fashion. The 1H and 13C NMR spectra of the complexes recorded in CD3CN suggest that the complexes adopt in solution a similar structure to that observed for the Nd complex in the solid state. The [Ln(L)(NO3)3] and [Ln(L)(NO3)2]+ complexes were characterized by density functional theory (DFT) calculations (B3LYP model). The structures obtained from these calculations for La, Ce, Pr, and Nd are in good agreement with the experimental solid-state structures. The relative stabilities of the [Ln(L)(NO3)2]+ complexes with respect to the [Ln(L)(NO3)3] ones (Ln = La, Nd, Gd, Ho, or Lu) were studied both in vacuo and in acetonitrile solution (PCM model) at the same computational level. Our calculations indicate that in solution the [Ln(L)(NO3)2]+ species is the most stable one along the whole lanthanide series, in agreement with the NMR spectroscopic data.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] The Role of Functionalisation, Asymmetry and Shape of a New Macrocyclic Compartmental Ligand in the Formation of Mononuclear, Homo- and Heterodinuclear Lanthanide(III) ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2009Sergio Tamburini Abstract The compartmental [1+1] macrocycle H3L, obtained by self-condensation of the formyl precursor 3,3,-(3,6-dioxaoctane-1,8-diyldioxy)bis(2-hydroxybenzaldehyde) with the amine precursor N,N -bis(2-aminoethyl)-2-hydroxybenzylamine, contains one inner ON3O2 Schiff base and one outer O2O4 crown-like chamber. According to the experimental conditions it forms, by a template process, the stable mononuclear complexes Ln(H3L)(Cl)2(CH3COO)·nS·mHCl or [Ln(L)]·nS (Ln = La, Lu, Y, Yb, Er, Dy, Tb, Gd, Eu, Ce) with the lanthanide(III) ion encapsulated in the crown-ether-like and in the Schiff base site. The mononuclear complexes Ln(H3L)(Cl)2(CH3COO)·nS·mHCl, by further complexation with a different lanthanide(III) ion, give rise to the related heterodinuclear complexes [LnLn,(L)(Cl)2(CH3COO)]·nS while the homodinuclear and the heterodinuclear complexes [Ln2(L)](Cl)3·nH2O and [LnLn,(L)](Cl)3·nS could be prepared by a template reaction using the appropriate molar ratio of reactants. Their properties have been studied by using SEM-EDS microscopy, IR and NMR spectroscopy and their compositions confirmed by thermal and ESI-Mass spectrometric analyses. In the heterodinuclear complexes, the site occupancy of the different lanthanide(III) ions was determined by 1H and 13C NMR spectroscopy in CD3OD or (CD3)2SO , it was found that heterodinuclear complexation occurs in methanol with the smaller lanthanide(III) ion mainly coordinating to the Schiff base site and the larger lanthanide(III) ion to the crown site whereas, in dimethyl sulfoxide, demetalation of the weaker coordinated lanthanide(III) ion into the crown ether chamber occurs with the subsequent formation of mononuclear species in solution. The thermal decomposition of the heterodinuclear complexes forms the related mixed oxides, the stoichiometries and properties of which were determined by SEM-EDS microscopy and X-ray powder diffraction studies (XRD). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Aluminium Complexes of a Phenoxyimine Ligand with a Pendant Imidazolium Moiety: Synthesis, Characterisation and Evidence for Hydrogen Bonding in SolutionEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 35 2008Stefano Milione Abstract Novel alkylaluminium complexes (phim)AlMe2 (1) and(phimid)AlR2+Br, [R = Me (2), R = iBu (3)] bearing the Schiff base ligands 3,5- tBu2 -2-(OH)C6H2CH=NiPr (phim -H) and3,5- tBu2 -2-(OH)C6H2CH=NCH2CH2[CH(NCHCHNiPr)]Br(phimid -H·Br) have been prepared and fully characterised. Complexes 1,3 each have a tetrahedral structure, with the aluminium atom surrounded by the oxygen and nitrogen atoms of the chelating ligand and two alkyl groups. The structures of phimid -H·Br and of complex 1 have been determined by X-ray diffraction studies. Investigation of the solution structures of 1,3 by 1H NMR spectroscopy revealed that the coordinated phimid ligand is involved in hydrogen bonding with bromide anion. Treatment of 1 with B(C6F5)3 led smoothly to (phim)Al(C6F5)Me (4) by transfer of a C6F5 group from MeB(C6F5)3, to the initially formed coordinatively unsaturated cationic intermediate. In contrast, treatment of 2 with one equiv. of B(C6F5)3 afforded the cationic monomethyl species (phimid)AlMeBr+,MeB(C6F5)3, (5), stabilised by the coordination of the bromide anion acting as a Lewis base.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Base-Induced Formation of Two Magnesium Metal-Organic Framework Compounds with a Bifunctional Tetratopic LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2008Pascal D. C. Dietzel Abstract Two coordination polymers constructed from magnesium and the tetratopic organic linker 2,5-dihydroxyterephthalic acid are reported, denominated CPO-26-Mg and CPO-27-Mg. The organic component carries two different types of protic functional groups. The degree of deprotonation of the organic component can be regulated by the amount of sodium hydroxide employed in the synthesis, thus determining which of the compounds forms. In CPO-26-Mg, only the carboxylic acid groups of the linker are deprotonated and take part in the construction of the three-dimensional framework. The structure is non-porous, and its topology is based on the PtS net. In CPO-27-Mg, both the carboxylic acid and the hydroxy groups are deprotonated and involved in the construction of a microporous three-dimensional framework which is based on a honeycomb motif containing large solvent-filled channels. The metal atoms are arranged in chiral chains along the intersection of the honeycomb and contain one water molecule in their coordination sphere, which allows for the creation of coordinatively unsaturated metal sites upon dehydration. CPO-27-Mg is a potentially useful lightweight adsorbent with a pore volume of 60,% of the total volume of the structure and an apparent Langmuir surface area of up to 1030 m2,g,1. Its thermal stability was investigated by thermogravimetry and variable-temperature powder X-ray diffraction, which shows framework degradation to commence at 160 °C in air, at 235 °C under nitrogen, and at 430 °C in a dynamic vacuum. Thermogravimetric dehydration and re-hydration experiments at miscellaneous temperatures indicate that it is possible to obtain open metal sites in CPO-27-Mg, but the water is more tightly bound in this material than in the previously reported isostructural nickel compound.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Stereoselective Synthesis of the First Chatt-Type Bis(dinitrogen)-Molybdenum(0) Complex with a Tetraphosphane LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 21 2008René Römer Abstract The first Chatt-type Mo0 dinitrogen complex with a tetraphosphane ligand has been prepared and characterized by NMR as well as infrared and Raman spectroscopy. Importantly, the employed reaction route allows the stereospecific synthesis of this complex as trans -[Mo(N2)2(meso -prP4)] (prP4 = a tetraphos ligand with a central propylene bridge). The stereoselectivity in the reaction course is induced by the oxido-iodido-molybdenum(IV) precursor [Mo(O)I(prP4)]+ which directs both phenyl groups of the bridging P atoms of prP4 into a meso configuration. The paper establishes a general strategy to synthesize mononuclear Mo0 dinitrogen and related molybdenum complexes with multidentate phosphane ligands which has not been possible to date. Moreover, the obtained molybdenum tetraphos N2 complex should exhibit a higher thermodynamic stability in the reactions of the Chatt cycle of synthetic nitrogen fixation than the conventional bis(diphos) complexes, due to the linkage of the two diphosphane units by an alkyl bridge. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] An Atropo-Stereogenic Diphosphane Ligand with a Proximal Cationic Charge: Specific Catalytic Properties of a Palladium Complex ThereofEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2008Nathalie Debono Abstract A class of cationic diphosphane ligands combining phosphane and amidiniophosphane moieties is illustrated on the N -methyl,N -naphthylbenzimidazolium framework. The palladium(II) complex thereof is described and compared to the corresponding complex of the analogous neutral diphosphane. Contrary to first-level expectations, the N2C,P and N2CP,Pd bonds in the cationic diphosphane complex are not longer than those occurring in its neutral counterpart. In the cationic ligand, the proximal positive charge is indeed conjugated to one phosphanyl group, and the coordination scheme is tentatively interpreted by resonance of the phosphane,metal dative bond (+N2C,P:,[Pd]) with a carbene,phosphenium dative bond (N2C:,[+P:,Pd]). Despite this peculiar structural feature, the electronic , donation (vs. , acceptation) towards the palladium centre remains lowered in the cationic ligand. This specific property can be a priori valuable in a catalytic process where oxidative addition is not the limiting step. It is indeed shown that although the neutral complex is more active in Suzuki coupling reactions, the cationic complex is more active in Sonogashira-type coupling reactions involving predissociated halide substrates, namely an acyl chloride. These likely atropo-chiral ligands deserve to be resolved for application in asymmetric catalysis.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Luminescent Gold(I) and Copper(I) Phosphane Complexes Containing the 4-Nitrophenylthiolate Ligand: Observation of ,,,* Charge-Transfer EmissionEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2008Cheng-Hui Li Abstract Gold(I) and copper(I) phosphane complexes containing the 4-nitrophenylthiolate ligand, namely [(PCy3)Au(SC6H4NO2 -4)] (1) (PCy3 = tricyclohexylphosphane), [Au2(,-dcpm)(SC6H4NO2 -4)2] (2) [dcpm = bis(dicyclohexylphosphanyl)methane], [Au2(,-dppm)(SC6H4NO2 -4)2] (3) [dppm = bis(diphenylphosphanyl)methane], and [(,2 -SC6H4NO2 -4)2(,3 -SC6H4NO2 -4)2(CuPPh3)4] (4), were prepared and characterized by X-ray crystal analysis. All of these complexes show an intense absorption band with ,max at 396,409 nm attributed to the intraligand (IL) ,(S),,*(C6H4NO2 -4) charge-transfer transition. The assignment is supported by the results of DFT and TDDFT calculations on the model complexes [PH3Au(SC6H4NO2 -4)] and [(,2 -SC6H4NO2 -4)2(,3 -SC6H4NO2 -4)2(CuPH3)4]. The emissions of solid samples and glassy solutions (methanol/ethanol, 1:4, v/v) of 1,4 at 77 K are assigned to the [,(S),,*(C6H4NO2 -4)] charge-transfer excited state. Metallophilic interactions are not observed in both solid state and solutions of complexes 1,3. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Influence of the Diketonato Ligand on the Cytotoxicities of [Ru(,6 - p -cymene)(R2acac)(PTA)]+ Complexes (PTA = 1,3,5-triaza-7-phosphaadamantane)EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 10 2008Carsten A. Vock Abstract A series of compounds of general formula [Ru(,6 - p -cymene)(R2acac)(PTA)][X] (R2acac = Me2acac, tBu2acac, Ph2acac, Me2acac-Cl; PTA = 1,3,5-triaza-7-phosphaadamantane; X = BPh4, BF4), and the precursor to the Me2acac-Cl derivative [Ru(,6 - p -cymene)(Me2acac-Cl)Cl], have been prepared and characterised spectroscopically. Five of the compounds have also been characterised in the solid state by X-ray crystallography. The tetrafluoroborate salts are water-soluble, quite resistant to hydrolysis, and have been evaluated for cytotoxicity against A549 lung carcinoma and A2780 human ovarian cancer cells. The compounds are cytotoxic towards the latter cell line, and relative activities are discussed in terms of hydrolysis (less important) and lipophilicity, which appears to exert the dominating influence. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [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] A Polymer-Bound Oxidovanadium(IV) Complex Prepared from an L -Cysteine-Derived Ligand for the Oxidative Amination of StyreneEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2008Mannar R. Maurya Abstract The ligand H2sal-cys (I) derived from salicylaldehyde and L -cysteine has been covalently bonded to chloromethylated polystyrene cross-linked with 5,% divinylbenzene. Upon treatment with [VO(acac)2] in dimethylformamide (DMF) the polystyrene-bound ligand PS-H2sal-cys (II) gave the oxidovanadium(IV) complex, PS-[VO(sal-cys)·DMF] (1). The corresponding neat complex, [VO(sal-eta)]2 (2), has also been prepared similarly in methanol. These complexes have been characterised by IR, electronic, EPR spectroscopic studies, magnetic susceptibility measurements and thermal as well as scanning electron micrographs studies. Complex [VO(sal-eta)]2 exhibits a medium intensity band at 980 cm,1 in the IR spectrum due to ,(V=O) stretch. Broad features of the EPR spectrum for the neat complex along with magnetic susceptibility studies suggest the presence of antiferromagnetic exchange interaction between two vanadium centers in close proximity. Both complexes catalyze the oxidative amination of styrene, in mild basic conditions, with secondary amines (diethylamine, imidazole, and benzimidazole) and gave a mixture of two aminated products in good yields. Amongst the two aminated products, the anti-Markovnikov product is favored over the Markovnikov one due to the steric hindrance posed by the secondary amines. The polymer-anchored heterogeneous catalyst is free from leaching during catalytic action and recyclable.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] A New Pentadentate Ligand Forms Both a Di- and a Mononuclear MnII Complex: Electrochemical, Spectroscopic and Superoxide Dismutase Activity StudiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 28 2007Federico Cisnetti Abstract The X-ray crystal structure of the dinuclear complex[1(PF6)2] derived from a new ligand bearing both imidazole and phenolato moieties, namely N -(2-hydroxybenzyl)- N,N,-bis[2-(N -methylimidazolyl)methyl]ethane-1,2-diamine (LH), is described and its properties in organic solvent (CH3CN) investigated (EPR, electrochemistry). [1(PF6)2] is shown to be a mononuclear MnII species in aqueous solution and displays an efficient SOD-like activity, as measured by the McCord,Fridovich assay performed both in conventional phosphate buffer and in a noncoordinating buffer (PIPES). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Conformational Flexibility in a Carbobicyclic Diphosphinite LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 20 2007Ian J. S. Fairlamb Abstract An unsymmetrical bicyclo[3.2.0]heptanyl diphosphinite ligand, FLEXIphosO, shows flexible coordination modes to palladium centres. The X-ray crystal structure for [Pd02(P,P,)3] has been determined which reveals that the bicyclic backbone of the FLEXIphosO ligand exists in an exo -envelope conformation. The change in conformation stands in stark contrast to that observed in mononuclear neutral and cationic palladium(II) complexes containing the FLEXIphosO ligand, where an endo -envelope is observed in solution and in the solid-state. Theoretical studies provide an insight into the relative stability of palladium(0) complexes containing the FLEXIphosO ligand. Another large spanning angle ligand, SPANphos, does not form a similar palladium(0) dimer complex under identical reaction conditions, highlighting the unusual behaviour of the FLEXIphosO ligand.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Tris(dibenzo[a,d]cycloheptenyl)phosphane: A Bulky Monodentate or Tetrapodal LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2007Urs Fischbach Abstract The tetradendate phosphane tris(5H -dibenzo[a,d]cyclohepten-5-yl)phosphane (trop3P, 1) was synthesized from tris(trimethylsilyl)phosphane and 5-chloro-5H -dibenzo[a,d]cycloheptene. Sulfurization of 1 with elemental sulfur led to trop3P=S. Complexes of 1 with AgI, AuI, RhI, IrI, and PdII were prepared. The structures of trop3P (1), trop3P=S (2), [AgCl(trop3P)] (3), [Au(trop3P)(MeCN)]PF6 (5), [RhCl(trop3P)] (6) and [Pd(trop3P)(H2O)](OTf)2 (9) were determined by X-ray diffraction studies. In the coinage metal complexes, 1 serves as monodentate extremely bulky ,1 -phosphane ligand (cone angle ca. 250°). In the RhI, IrI, and PdII complexes, 1 acts as tetradendate ligand. CP MAS NMR spectroscopy shows that the span of the chemical shift tensor increases in 7, 6, and 9 in this order (, = 310 ppm, 410 ppm, 465 ppm) and contains two strongly deshielded components, which are responsible for the unusual high frequency isotropic shift of the 31P resonances. This property correlates inversely with the metal to olefin backbonding (M,C=Ctrop) and ,(31P) decreases with increasing M,C=Ctrop in the order 9 (, = 260 ppm) > 7 (, = 196 ppm) > 6 (, = 135 ppm) > 3 (, = ,30.9 ppm). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] A Magnetostructural and Electrochemical Study of CuII and FeIII Complexes Containing a Tetradentate Aminebis(phenolate) Ligand with a Pendent Tetrahydrofuran GroupEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 16 2007Elham Safaei Abstract Ligating properties of a tetradentate ligand 2-{bis[(3,5-di- tert -butyl-2-hydroxybenzyl)amino]methyl}tetrahydrofuran,H2L, with [O,O,N,O]-donor atoms towards CuII and FeIII are described. The ligand H2L yields both mononuclear LFeIII(acac) (1) and dinuclear [L2FeIII2(,-OCH3)-(,-OH)] (2), [L2FeIII2(,-C2O4)] (3) and [L2CuII2] (4) complexes, which were characterized by various physical techniques, including X-ray diffraction, Mössbauer, electrochemical and magnetic susceptibility (2,290 K) measurements. That the electrochemical oxidations are ligand-centered, i.e. formation of phenoxyl radicals from the coordinated phenolates, have been shown by voltammetric methods. Complexes 2,4 display antiferromagnetic exchange coupling of the neighbouring metal centers. Comparison of the evaluated weak exchange coupling constants (J) with the literature values leads to the conclusion that the angle Cu,O,Cu, is not the only determinant for the nature of the exchange coupling and the capability of the bridging ligands as mediators for spin coupling in case of FeIII follows the order phenoxide , methoxide > hydroxide. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Synthesis and Characterization of Novel Titanium, Germanium, and Tin Silazane Complexes Bearing a Cyclohexasilazanetriido LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2007Christian Lehnert Abstract Novel heterometallic silazane complexes were synthesized by the reaction of 1-lithio-2,2,4,4,6,6-hexamethylcyclotrisilazane Li(HMCTS)H2 with the tetrachloride salts of titanium and germanium as well as by the reaction of 1,1,3,3,5,5-hexamethylcyclotrisilazane H3(HMCTS) with tin tetrachloride and excess triethylamine. The products [H3(DMCHS)TiCl] (1), [H3(DMCHS)GeCl] (2), and [H3(DMCHS)SnCl] (3) {H3(DMCHS) = 2,2,4,4,6,6,8,8,10,10,12,12-dodecamethylcyclohexasilazane-1,5,9-triido} were characterized by 1H-, 13C-, 14N-, and 29Si NMR spectroscopy, elemental analyses and single-crystal X-ray structure analyses. The complexes have a surprising and interesting structure, that of a new dodecamethylcyclohexasilazane system with the Ti, Ge, or Sn atom in the center. These metal atoms are coordinated by one chlorine atom and three nitrogen atoms. The metal centers are part of three six-membered hetero-silazane rings. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Synthesis, Structure and Magnetic Properties of a Tetranuclear Copper(II) Complex on the Basis of a 2-Substituted Glucopyranoside Schiff Base Ligand,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 17 2006Anja Burkhardt Abstract Condensation of a derivatized 2-aminoglucose fragment with salicylaldehyde affords the new sugar-based Schiff base ligand benzyl 4,6- O -benzylidene-2-deoxy-2-salicylideneamino-,- D -glucopyranoside (H2L). The reaction of the dibasic ligand H2L with [Cu(CH3COO)2]·H2O leads to the formation of the tetranuclear copper(II) complex [{Cu(L)}4] (3) by a self-assembly process. The X-ray structural analysis of complex 3 which crystallizes together with two molecules of chloroform and one molecule of ethanol in the space group P212121 revealed for all copper atoms a NO3 coordination environment with a square-planar geometry. The tetranuclear molecule 3 consists of four chiral building blocks {Cu(L)} with the rare 2,3-coordination of the trans -configured donor atoms of the sugar backbone. The observed coordination mode of the building blocks exemplifies how chitosan-derived polysaccharide ligands can act as a chiral support for transition-metal complexes. The C-3 alcoholate oxygen atoms of the carbohydrate unit is bridging adjacent {Cu(L)} moieties resulting in an eight-membered Cu4O4 ring with a boat-like conformation. Temperature-dependent magnetic measurements of 3 indicate moderate antiferromagnetic interactions between the four copper(II) ions with a coupling constant of J = ,130 cm,1.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Molecular Structures and NMR Studies of Lithium and Germanium(II) Complexes of a New Chelating Amido,Imino Ligand Obtained by Addition of nBuLi to 1,2-Bis(arylimino)acenaphthene,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 16 2006Igor L. Fedushkin Abstract The reaction of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian, 1) with 1 equiv. of nBuLi in diethyl ether or with 2 equiv. of nBuLi in hexane produces [{dpp-bian(nBu)}Li(Et2O)] (3) and [{dpp-bian(nBu)Li}nBuLi]2 (4), respectively. Complexes 3 and 4 are formed by the transfer of an nBu anion to one of the imine carbon atoms of the dpp-bian ligand. Treatment of 3 and 4 with H2O affords the C -alkylated N -protonated amino-imino compound dpp-bian(H)(nBu) (5). The reaction of 3 with GeCl2(dioxane) affords the three-coordinate germylene complex [{dpp-bian(nBu)}GeCl] (6). The molecular structures of 3,6 were determined by single-crystal X-ray structure analysis. The lack of symmetry in the alkylated bian system in 3,6 causes the non-equivalence of all protons except those of the CH3 groups of the iPr substituents. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] | ||||||||||||||||||||||||||||||||||||||||||||||