Bidentate Chelating Research Articles

Fe-Catalyzed Aliphatic C-H Methylation of Glycine Derivatives and Peptides.

Direct and selective C-H methylation is a powerful tool with which to install methyl groups into organic molecules, and is particularly useful in pharmaceutical chemistry. However, practical methods for such modification of biologically interesting targets have been rarely developed. We here report an iron-catalyzed C(sp3 )-H methylation reaction of glycine derivatives, peptides and drug-like molecules in an alcohol in the presence of di-tert-butyl peroxide. A readily available iron catalyst plays multiple roles in the transformation, which accelerates oxidation of C-N bonds to C=N double bonds, activates imine intermediates as Lewis acids by bidentate chelation, and at the same time facilitates cleavage of the peroxide to generate methyl radicals. A variety of methylated N-aryl glycine derivatives and peptides were obtained in good yield and with excellent chemo- and site-selectivity. This reaction is scalable, easily managed, and can be completed within 1-2 h. It features an economic, bio-friendly catalyst, a green solvent and low toxic reagents, and will provide effective access to precise C-H modification of biomolecules and natural products.

Functionalization of anatase nanoparticles with Glutaric acid and their photochemical and photocatalytic properties under visible light

Charge transfer complexes (CTCs) formed between TiO2 and chelating ligands have attracted extensive attention for photocatalytic applications under visible radiation due to their increased visible light absorption. Different TiO2-based CTCs have been widely studied. However, the sensitization of TiO2 to visible light by functionalization with glutaric acid (TiO2-GA) and its photocatalytic performance under visible light radiation have not yet been investigated, as far as the authors know. In this study, visible-light-sensitive TiO2-GA nanomaterials were synthesized via sol-gel and calcined under static air at 270 °C. The as-prepared TiO2-GA CTCs were characterized by XRPD, FTIR, TGA, DRS, PL, EPR and XPS techniques. FTIR data supported the formation of the CTC through bidentate chelating interaction between TiO2 and GA. TiO2-GA CTCs calcined at 270 °C under static air exhibited a long absorption tail in the visible light spectrum mainly due to the formation of F+ centers. The high content of GA molecules bounded to the TiO2 surface was not beneficial for photocatalytic performance of the TiO2-GA CTCs, since these molecules reduced the active sites on the nanostructure surface, resulting in a lower production of superoxide radicals by the TiO2-GA CTCs. Our findings indicated that: a) TiO2-GA CTCs are capable to degrade antibiotic liquid pollutants via interactions with superoxide radicals and also, b) provided fundamental insights into the influence of bulk Ti3+ defects and bulk oxygen vacancies on photocatalytic performance and photochemical properties of TiO2-based CTCs.

Synthesis, characterization and study of mercury(II) complexes with phosphine and heterocyclic thiones

Many new mixed ligand complexes of mercury(II) have been synthesized with LH = 4,5-(diphenyl)-1,2,4-triazole-3-thione (diptSH) and tertiary phosphines as co-ligands. The compounds have been characterized by elemental analyses, IR, UV–Vis, molar conductivity, and NMR spectroscopy. In the binuclear complexes (2-5), both Hg atoms have tetrahedral geometry, the Hg atom bonded to three halide ions and one thione ligand (LH) through the sulfur atom. The complex (6) show that thiolate ligand(diptS-) is coordinated as monodentate through the sulfur atom. The dppm behave as bidentate bridging ligand to bonded two Hg(II) ions in the complex (7), Whereas in the complexes (7-10), the thionlate ligand bonded as a monodentate fashion via the sulfur atom, while the diphosphines ligands coordinated as bidentate chelating ligands, and the geometry around the Hg center ion is tetrahedral. And in the complexes (11 and 12), the phosphine bonded as monodentate ligand, and the thionlate bonded via the sulfur atom as monodentate to give tetrahedral complexes

Synthesis of silver complexes with chelating bidentate N‐heterocyclic ligands, their application in catalytic A3 coupling, and as antimicrobial agents

We present a synthesis of novel silver complexes stabilized by bidentate ligands based on N‐heterocyclic carbenes (NHC) linked with a bisamide linker. The ligand stabilizes the silver ion in a rare chelating mode. The synthesis of the complex depends on the equimolar ratio of the silver source and the ligand precursor. In case the excess of the silver source is used, the reaction leads to the formation of an unprecedented tetranuclear silver complex, stabilized by two equivalents of the ligand, where each of the silver atoms is coordinated by one NHC and one amide moiety. The silver complexes were applied as a catalyst in a multicomponent A3 coupling and proved to be a very efficient catalyst. The reaction provided desired products in yields up to 96%, and the use of low catalytic loading, as low as 0.1 mol%, was possible without significantly compromising the effectivity of the reaction. Moreover, the complexes showed broad spectra of antimicrobial activity, with minimal inhibitory concentrations in the range of 1 to 31 μg/ml against several Gram‐positive and Gram‐negative bacteria and fungi. Presented complexes represent synthetically challenging molecules, which show great applicability in catalysis and outstanding potential as antimicrobial agents.

Electrospray Mass Spectrometry to Study Combinatorial iClick Reactions and Multiplexed Kinetics of [Ru(N3)(N∧N)(terpy)]PF6 with Alkynes of Different Steric and Electronic Demand.

In a combinatorial approach, a family of ruthenium(II) azido complexes [Ru(N3)(N∧N)(terpy)]PF6 with terpy = 2,2':6',2″-terpyridine and N∧N as a bidentate chelator derived from 2,2'-biypridine and its 4,4'-disubstituted derivatives, 2,2'-bipyrimidine, and 1,10-phenanthroline were reacted with different internal and terminal alkynes to give access to a total of 7 × 7 = 49 triazolato complexes in a room-temperature catalyst-free iClick reaction. The reactants were mixed in a repurposed high-performance liquid chromatography (HPLC) autosampler, and the reaction progress was monitored by direct injection into an electrospray mass spectrometer. The ratio of the peak intensities of [Ru(N3)(N∧N)(terpy)]+ and [Ru(triazolato)(N∧N)(terpy)]+ was converted to a colored heat map for facile visual inspection of the conversion ratio. By automated multiple injections of the reaction mixture in fixed time intervals and plotting peak intensities over reaction time, pseudo-first-order rate constants were easily determined. Finally, nonoverlapping isotope patterns of the azido starting materials and triazolato products enabled multiplexed parallel determination of rate constants for four different ruthenium(II) azido complexes from a single sample vial, thereby reducing experiment time by 75%.

Influence of citrate/tartrate on chromite crystallization behavior and its potential environmental implications.

The ferrite process has been developed to purify wastewater containing heavy metal ions and recycle valuable metals by forming chromium ferrite. However, organic matter has an important influence on the crystallization behavior and stability of chromite synthesized from chromium-containing wastewater. We focused on the influence and effect mechanism of two typical organic acid salts (citrate (CA) and tartrate (TA)) on the process of chromium mineralization. It was found that the presence of organic matter leads to the increase of the residual content of Cr in CA system (0.50mmol/L) and TA system (0.61mmol/L) in the solution, and the removal of chromium was mainly due to the surface adsorption of Fe(III) hydrolysate. The decreased crystallinity of mineralized products is ascribed to the completion of organic compounds with Fe(II) and Fe(III), which hinders the formation of ferrite precursors. There was bidentate and monodentate chelation between -COO- and metal ions in the CA system and TA system respectively, which resulted in a stronger affinity between CA and iron. This study provides the underlying mechanism for Cr(III) solid oxidation by the ferrite method in an organic matter environment and is of great significance to prevent and control chromium pollution in the environment.

Pt phosphor-, oxygen-rich complexes: One pot synthesis, characterization, molecular docking and antiproliferative study

This work includes the synthesis of a series of O- and P- rich platinum complexes by the reaction of Pt+2 with tertiary phosphines (PPh3, dppm, dppe, dppp, dppf) and 3,4,5‑trimethoxybenzoic acid (HTMB) through a one-pot reaction. All complexes were characterized using FTIR, CHN, molar conductivity, 1H NMR and 31P NMR. The characterization results proved that the TMB ligand in all complexes behaves as a monodentate through the deprotonated oxygen atom. The phosphine ligands were associated to platinum center with chelating bidentate mode while PPh3 and dppm were behaved as monodentate and bridging bidentate ligands, respectively. The PPh3-containing complex (trans-[Pt(TMB)2(PPh3)2]) was used to examine its anticancer activity against A2780, SW620, HT29, A172, C6 and HeLa cell lines. The results proved that the TGI value was 40.33 ± 1.4, 18.05 ± 0.8, 48.91 ± 1.6, 44.43 ± 2.8, 51.03 ± 2.0 and 56.98 ± 2.1 for A172, C6, HeLa, A2780, SW620 and HT29, respectively. TGI values were better than those reported for the reference compound 5FU. The molecular docking proves that trans-[Pt(TMB)2(PPh3)2] have pi-alkyl hydrophobic interaction, carbon-hydrogen bonding, electrostatic interaction and pi-lone pair interaction with different amino acids.

A novel chelating bidentate NHC ligand based on the cationic (η5-cyclopentadienyl)(η6-arene)iron(II) motif

We here present the synthesis of a novel chelating N-heterocyclic carbene (NHC) ligand with the two NHC moieties bound to a cationic (η5-cyclopentadienyl)(η6-arene)iron(II) center and its coordination to palladium(II). Spectroscopic and spectrometric characterization, together with X-ray structural analyses, proves the molecular structure of these new organometallic compounds.

Embracing [XY3]m– and [XY4]m– Anions in Salts of [M(bpy)3]q+

[M(bpy)3]q+ cations (bpy = 2,2′-bipyridine) are archetypical coordination entities containing chelating bidentate N,N′-donor ligands. Each propeller-shaped cation is chiral, existing as a Δ or Λ enantiomer. The supramolecular chemistry of [M(bpy)3]q+ cations in the crystal is dominated by cation-anion interactions and, to a lesser extent, weaker non-covalent interactions. Analysis of the data for [M(bpy)3]q+ salts in the Cambridge Structural Database (CSD) reveals a ubiquitous motif in which homochiral sheets of cations generate cavities for the accommodation of anions. A series of related and common motifs in the solid-state structures of [M(bpy)3]q+ salts has been identified. One of the commonest motifs comprises a hexagon of six cations with anions either in the center or lying above and/or below the centroid.

Titanium(IV) Surface Complexes Bearing Chelating Catecholato Ligands for Enhanced Band-Gap Reduction

Protonolysis reactions between dimethylamido titanium(IV) catecholate [Ti(CAT)(NMe2)2]2 and neopentanol or tris(tert-butoxy)silanol gave catecholato-bridged dimers [(Ti(CAT)(OCH2tBu)2)(HNMe2)]2 and [Ti(CAT){OSi(OtBu)3}2(HNMe2)2]2, respectively. Analogous reactions using the dimeric dimethylamido titanium(IV) (3,6-di-tert-butyl)catecholate [Ti(CATtBu2-3,6)(NMe2)2]2 yielded the monomeric Ti(CATtBu2-3,6)(OCH2tBu)2(HNMe2)2 and Ti(CATtBu2-3,6)[OSi(OtBu)3]2(HNMe2)2. The neopentoxide complex Ti(CATtBu2-3,6)(OCH2tBu)2(HNMe2)2 engaged in further protonolysis reactions with Si-OH groups and was consequentially used for grafting onto mesoporous silica KIT-6. Upon immobilization, the surface complex [Ti(CATtBu2-3,6)(OCH2tBu)2(HNMe2)2]@[KIT-6] retained the bidentate chelating geometry of the catecholato ligand. This convergent grafting strategy was compared with a sequential and an aqueous approach, which gave either a mixture of bidentate chelating species with a bipodally anchored Ti(IV) center along with other physisorbed surface species or not clearly identifiable surface species. Extension of the convergent and aqueous approaches to anatase mesoporous titania (m-TiO2) enabled optical and electronic investigations of the corresponding surface species, revealing that the band-gap reduction is more pronounced for the bidentate chelating species (convergent approach) than for that obtained via the aqueous approach. The applied methods include X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and solid-state UV/vis spectroscopy. The energy-level alignment for the surface species from the aqueous approach, calculated from experimental data, accounts for the well-known type II excitation mechanism, whereas the findings indicate a distinct excitation mechanism for the bidentate chelating surface species of the material [Ti(CATtBu2-3,6)(OCH2tBu)2(HNMe2)2]@[m-TiO2].

Reactivity regulation for olefin metathesis-catalyzing ruthenium complexes with sulfur atoms at the terminal of 2-alkoxybenzylidene ligands.

For regulating the olefin metathesis (OM) activity of the Hoveyda-Grubbs second-generation complex (HG-II), the structural modification of the benzylidene ligand is a useful strategy. This paper reports the effect of a chalcogen atom placed at the end of the benzylidene group on the catalytic properties of HG-II derivatives, using complexes with a thioether or ether component in the benzylidene ligand (ortho-Me-E-(CH2)2O-styrene; E = S, O). Nuclear magnetic resonance and X-ray crystallographic analyses of the complex with a thioether moiety (E = S) proved the (O,S)-bidentate and trans-dichlorido coordination for the complex. A stoichiometric ligand exchange between HG-II and the benzylidene ligand (E = S) produced the corresponding complex with an 86% yield, confirming higher stability of the complex (E = S) than that of HG-II. Despite the bidentate chelation, the complex (E = S) exhibited OM catalytic activity, indicating the exchangeability of the S-chelating ligand with an olefinic substrate. The green solution color, a characteristic of HG-II derivatives, was retained after the complex (E = S)-mediated OM reactions, indicating high catalyst durability. Conversely, the complex (E = O) rapidly initiated OM reactions; however, it showed low catalyst durability. In the OM reactions conducted in the presence of methanol, the complex (E = S) exhibited higher yields than the complex (E = O) and HG-II: the S-coordination increased the catalyst tolerance to methanol. A coordinative atom (such as sulfur) placed at the terminal of the benzylidene ligand can precisely regulate the reactivity of HG-II derivatives.

Cluster size dependent coordination of formate to free manganese oxide clusters.

The interaction of free manganese oxide clusters, MnxOy+ (x = 1-9, y = 0-12), with formic acid was studied via infrared multiple-photon dissociation (IR-MPD) spectroscopy together with calculations using density functional theory (DFT). Clusters containing only one Mn atom, such as MnO2+ and MnO4+, bind formic acid as an intact molecule in both the cis- and trans-configuration. In contrast, all clusters containing two or more manganese atoms deprotonate the acid's hydroxyl group. The coordination of the resulting formate group is strongly cluster-size-dependent according to supporting DFT calculations for selected model systems. For Mn2O2+ the co-existence of two isomers with the formate bound in a bidentate bridging and chelating configurations, respectively, is found, whereas for Mn2O4+ the bidentate chelating configuration is preferred. In contrast, the bidentate bridging structure is energetically considerably more favorable for Mn4O4+. This binding motif stabilizes the 2D ring structure of the core of the Mn4O4+ cluster with respect to the 3D cubic geometry of the Mn4O4+ cluster core.

Interesting chemical and physical features of the products of the reactions between trivalent lanthanoids and a tetradentate Schiff base derived from cyclohexane-1,2-diamine.

The initial use of a tetradentate Schiff base (LH2) derived from the 2 : 1 condensation between 2-hydroxyacetophenone and cyclohexane-1,2-diamine in 4f-metal chemistry is described. The 1 : 2 reaction of Ln(NO3)3·xH2O (Ln = lanthanoid or yttrium) and LH2 in MeOH/CH2Cl2 has provided access to isostructural complexes [Ln(NO3)3(L'H2)(MeOH)] in moderate to good yields. Surprisingly, the products contain the corresponding Schiff base ligand L'H2 possessing six aliphatic -CH2- groups instead of the -CH-(CH2)4-CH- unit of the cyclohexane ring, i.e. an unusual ring-opening of the latter has occurred. A mechanism for this LnIII-assisted/promoted LH2 → L'H2 transformation has been proposed assuming transient LnII species and a second LH2 molecule as the H2 source for the reduction of the cyclohexane moiety. DFT calculations provide strong evidence for the great thermodynamic stability of the products in comparison with analogous complexes containing the original intact ligand. The structures of the PrIII, SmIII, GdIII, TbIII, and HoIII complexes have been determined by single-crystal X-ray crystallography. The 9-coordinate LnIII centre in the molecules is bound to six oxygen atoms from the three bidentate chelating nitrato groups, two oxygen atoms that belong to the bidentate chelating organic ligand, and one oxygen atom from the coordinated MeOH group. In the overall neutral bis(zwitterionic) L'H2 ligand, the acidic H atoms are clearly located on the imino nitrogen atoms and this results in the formation of an unusual 16-membered chelating ring. The coordination polyhedra defined by the nine donor atoms around the 4f-metal-ion centres can be best described as distorted, spherical capped square antiprisms. The EuIII, TbIII, and DyIII complexes exhibit LnIII-based luminescence in the visible region, with the coordinated L'H2 molecule acting as the antenna. Ac magnetometry experiments show that the DyIII member of the family behaves as an SIM at zero field and under external dc fields of 0.1 and 0.2 T without the enhancement of the peaks' maxima, suggesting that QTM is not the relaxation path. The GdIII complex behaves, rather unexpectedly, as a SIM with two different magnetic relaxation paths occurring at very close temperatures; this behaviour is tentatively attributed to a very small axial zero-field splitting (D ∼ 0.1 cm-1), which cannot be detected by magnetization or susceptibility experiments. The prospects of the present, first results in the lanthanoid(III)-LH2 chemistry are discussed.

Synthesis, structure and magnetic properties of two bis(oxalato)cuprate(ii) salts with pyridinium type counter ions

In the Cu(ii) oxalate salts of (C5H7N2O)2[Cu(C2O4)2] 1 and C13H16N2[Cu(C2O4)2] 2, the oxalate adopts different coordination modes: the common bidentate chelating oxalate in 1 and the relatively scarce μ-oxalato-κ3O1,O2:O1′ in 2.

Реакции пентафенил- и пента(пара-толил)сурьмы с ферроцендикарбоновой кислотой

In reactions of pentaphenyl- and penta(para-tolyl)antimony with ferrocene dicarboxylic acid (molar ratios 1:1 and 2:1) in toluene (20 С, 24 h), hydrogen in one or two carboxylate groups is replaced with formation of tetraarylantimony ferrocene carboxylates HOOС5H4FeС5H4C(O)OSbPh4 (1), HOOС5H4FeС5H4C(O)OSbTol4 (2), Ph4SbC(O)OC5H4FeС5H4C(O)OSbPh4 (3) and p-Tol4SbC(O)OC5H4FeС5H4C(O)OSbTol4 (4), yielding up to 83 %. Compounds 1–4 have been identified by elemental analysis, IR spectroscopy, and X-ray diffraction analysis for 4. X-ray diffraction analysis of complex 4 has been performed on a D8 Quest Bruker automatic four-circle diffractometer (Mo Kα radiation, λ = 0.71073 Å, graphite monochromator ) at 293 K. Crystallographic characteristics of compound 4: monoclinic system, space group P21/c, a = 17.227(17), b = 11.064(9), c = 30.59(3) Å, β = 100.00(4) deg., V = 5742(9) Å3, Z = 4, calc = 1.440 g/cm3, 2 6.02-49.08 deg., total reflections 124343, independent reflections 9436, number of refined parameters 684, Rint = 0.1051, GOOF 1.094, R1 = 0.0536, wR2 = 0.1309, residual electron density (max/min) 0.88/1.21 e/Å3. According to the X-ray diffraction analysis data, in crystal 4 coordination of the antimony atoms is distorted octahedral due to the fact that the carboxylate ligand is a bidentate chelating ligand. The diagonal angles in the two octahedra are 146.4(2), 154.0(3), 171.0(2) and 147.4(2), 154.8(2), 166.9(2). The SbO distances are 2.296(5), 2.502(5) Å and 2.289(5), 2.453(5) Å, the SbC bonds are significantly different (2.146(7)2.166(7) and 2.123(6)2.165(7) Å). The structural organization of the crystal is mainly due to the interactions of the СН•••-type.

Three new MnII-[MoIII(CN)7]4- molecular magnets constructed from chiral bidentate chelating ligands.

Three new cyanide-bridged compounds {[Mn((S,S)-Dpen)]3[Mn((S,S)-Dpen)(H2O)][Mo(CN)7]2·4H2O·4C2H3N}n (1-SS), {[Mn((R,R)-Dpen)]3[Mn((R,R)-Dpen)(H2O)][Mo(CN)7]2·4.5H2O·4C2H3N}n (1-RR), and {[Mn(Chxn)][Mn(Chxn)(H2O)0.8][Mo(CN)7]·H2O·4C2H3N}n (2) (SS/RR-Dpen = (S,S)/(R,R)-1,2-diphenylethylenediamine and Chxn = 1,2-cyclohexanediamine) have been successfully synthesized from the self-assembly reaction of the [MoIII(CN)7]4- unit, the MnII ions, and two chiral bidentate chelating ligands. Single-crystal structure determinations show that compounds 1-SS and 1-RR containing ligands SS/RR-Dpen are enantiomers and crystallize in the chiral space group P21. On the other hand, compound 2 crystallizes in the achiral centrosymmetric space group P1̄ due to the racemization of the SS/RR-Chxn ligands during the growth of the crystals. Despite their different space groups and ligands, all three compounds exhibit similar framework structures consisting of cyano-bridged MnII-MoIII two-dimensional layers separated by the bidentate ligands. The circular dichroism (CD) spectra have further demonstrated the enantiopure character of compounds 1-SS and 1-RR. Magnetic measurements revealed that all three compounds display ferrimagnetic ordering with similar critical temperatures of about 40 K. The chiral enantiomers 1-SS and 1-RR exhibit the magnetic hysteresis loop with a coercive field of about 8000 Oe at 2 K, which is by far the highest for all known MnII-[MoIII(CN)7]4- magnets. Analyses of their structures and magnetic properties indicated that their magnetic properties depend on the anisotropic magnetic interactions between the MnII and MoIII centers, which are closely related to the C-N-M bond angles.

Mixed Ligand Complexes of Cobalt(II): Synthesis, Reactivity, Physico-Chemical and Spectroscopic Studies

The mixed ligand complexes of Co(II) metal ions with some heterocyclic nitrogen bases along with 1-cyano-1-carboethoxyethylene-2,2-dithiolate ion (CED2−) of the compositions, Co(N-N)(CED)·2H2O [N-N = o-phen/2,2′-bipy] and Co(N-N)(CED)L2 [N-N = o-phen/2,2′-bipy, CED2– = 1-cyano-1- carboethoxyethylene-2,2-dithiolate, L = γ-picoline (γ-pic), β-picoline (β-pic), α-picoline (α-pic), pyridine (py)] were characterized and isolated by analytical data as well as physico-chemical methods for example infrared spectroscopy, electronic, magnetic susceptibility, molar conductance. The complexes are soluble in coordinating solvents like DMSO and DMF and decompose below 250 ºC. The synthesized complexes in DMF solution are non-electrolytic as shown by their molar conductance data. The calculated magnetic moments suggest that the synthesixed cobalt(II) compounds are paramagnetic and produce a low-spin environment for the Co(II) ion. Thermal studies reveal that Co(N-N) contains two coordinated water molecules (CED)·2H2O. Electronic spectra of cobalt(II) complexes with mixed ligands in DMF solution are consistent with distorted octahedral stereochemistry. The IR studies indicates that the CED2- ion exhibits bidentate chelating behaviour and that heterocyclic nitrogen donors coordinate to Co atoms (II). Reaction with heterocyclic nitrogen donors (γ-picoline, β-picoline, α-picoline, pyridine) signifying the ligand exchange reaction.

N-aryloxide-amidinate group 4 metal complexes.

A N-aryloxide-amidine ligand (H3L), integrating phenoxide (PhO-) and amidine ligands through methylene linkers, has been synthesized from 2-(aminomethyl)-6-(tert-butyl)phenol in two steps. Upon reacting the deprotonated H3L ligand with group 4 metal chloride MIVCl4, a corresponding (LMIV-Cl)2 dimer could be obtained. The coordination modes exhibit variation depending on the radius of the metal ions. In the case of (LTiIV-Cl)2, the two ArO- arms from the same ligand bond to two different Ti(IV) centers, while in the case of (LZrIV/HfIV-Cl)2, both ArO- arms coordinate with the same metal center. Moreover, the two C-N bonds in the amidinate moiety are localized in (LTiIV-Cl)2, whereas they delocalize in (LZrIV-Cl)2. Notably, (LHfIV-Cl)2 could further react with one equivalent of HfCl4, yielding the binuclear metal azide in the presence of KN3 and LiCl, where the coordination mode of the amidinate moiety changed from the bidentate chelating type to the bimetallic bridging coordination.

N-(Aryl)pyrrole-2-aldimine complexes of ruthenium: synthesis, structure, and spectral and electrochemical properties

Reaction of N-(4′-R-phenyl)pyrrole-2-aldimines (HL-R) with [Ru(dmso)4Cl2] in refluxing toluene affords complexes of type [Ru(L-R)2(dmso)2]. The two dmso's can be substituted by a chelating bidentate ligand such as bpy (or phen).

Incorporating Trimethylaluminium into the Structures of Alkali Metal (Li, Na, K, Cs) dihydropyridines

AbstractCo‐complexation of equimolar amounts of 1‐alkali‐metal‐2‐tertbutyldihydropyridines with AlMe3 in the presence of a polydentate N‐donor ligand has delivered four crystallographically verified alkali‐metal aluminates [donor⋅AM(μ‐tBuDHP)AlMe3]n (1, AM=Li, donor=TMEDA, n=1; 2, AM=Na, donor=PMDETA, n=1; 3, AM=K, donor=PMDETA, n=2; 4, AM=Cs, donor=PMDETA, n=∞; TMEDA=N,N,N′,N′‐tetramethylethylenediamine; PMDETA=N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine). While the monomeric complexes (1, 2) and the polymeric complex (4) are thermally stable, the dimeric complex (3) undergoes a disproportionation process yielding the known ion‐separated homoanionic complex [K ⋅ (PMDETA)2]+ [AlMe4]− (3 a). Utilizing TMEDA as the N‐donor resulted in the same disproportionation, but gave rise to two distinct solid‐state aggregated forms of aluminate [K ⋅ (TMEDA)2]+ [AlMe4]−, namely monomeric (3 b) and polymeric (3 b′) polymorphs, in which the anionic moiety acts as a bidentate chelator or monodentate bridge respectively to the potassium cationic moieties.