Nucleophilic cyclocarbenes as ligands in metal halides and metal oxides

The nucleophilic cyclocarbene 1,3-dimethylimidazolin-2-ylidene (1) reveals universal ligand properties in metal coordination chemistry: in addition to the well-known stabilization of low oxidation-state transition metal fragments, this particular class of carbenes also coordinates with metal halides and metal oxides thus resembling the properties of conventional ether (O), amine (N), and phosphane (P) ligands. Complexes of titanium(IV), zirconium(IV), hafnium(IV), vanadium(II), niobium(IV), tantalum(IV) of general formula MX_nL_m (3a–f) and the rhenium(VII) of formula CH₃ReO₃L₂ (3g) are reported (L = 1,3-dimethylimidazolin-2-ylidene).     

Sulfenamides as ligands in transition metal chemistry Pentacarbonyl(Sulfenamide)Chromium(0) Complexes

The complexes Cr(CO)₅(R′SNR₂) [R′ = CH₃; NR₂ = N(CH₃)₂, N(C₄H₈)O. R′ = C₆H₅; NR₂ = N(CH₃)₂, N(C₄H₄)O, N(CH₂? C₆H₅)₂, N(C₆H₁₁)₂] have been prepared by reaction of the sulfenamides with Cr(CO)₅ · THF and characterized by analytical and spectroscopic methods. The IR, ¹H-NMR, UV-VIS, and mass spectra of the complexes support the coordination of the sulfenamide via the sulfur atom. π-acceptor abilities of sulfenamides in the prepared coordination compounds, determined from IR and UV-VIS data, were compared with those of other divalent sulfur conpounds.     

Nucleophilic ring opening transformations of bridging thietane ligands in metal carbonyl cluster complexers

Recent studies of the nucleophilic ring opening reactions of bridging thietane ligands in metal cluster complexes are reviewed.     

水/油型微乳液中球形及棒状钛酸锶钡纳米粒子的控制合成

Barium strontium titanate nanoparticles with spherical and rod-like morphologies were synthesized in water/Triton X-100/n-hexanol/cyclohexane quaternary reverse microemulsion solution. The influences of the molar ratio of water to surfactant (ω₀) and the concentration of reactants on the morphology and size of barium strontium titanate nanoparticles were studied. The structure, compositions and morphology of the prepared products were characterized by XRD, SAED, ICP, EDS and TEM. The results show that the obtained Ba_0.7Sr_0.3TiO₃ spherical nanoparticles with diameters of 20～100 nm and the Ba_0.7Sr_0.3TiO₃ nanorods with diameters of 70～120 nm and lengths up to 600～800 nm are a single crystal, with a cubic phase. The molar ratio for barium, strontium and titanate in products is about 0.7:0.3:1.     

Complexes of quinolone drugs norfloxacin and ciprofloxacin with alkaline earth metal perchlorates

The interaction of quinolone drugs Norfloxacin (NR) and Ciprofloxacin (CP) with magnesium, calcium and barium perchlorates was investigated. Solid complexes, obtained as products of this interaction, were isolated and characterized by elemental and thermal analysis, FT-IR spectral and electrical conductivity measurements. The spectral studies of the isolated complexes suggest that NR and CP act as bidentate ligands that bind through one carboxylic oxygen atom and the exocyclic carbonyl oxygen atom. The obtained results indicate the formation of the complexes of the following formulas: [M(CP)₂](ClO₄)₂·xH₂O and [M(NR)₂](ClO₄)₂·xH₂O, where M = Mg(II), Ca(II), and Ba(II).     

Intergenerational continuity as a key factor for efficient development of organic chemistry and metal complex catalysis in Russia

Russian Journal of Organic Chemistry -     

Diol-type ligands as central 'players' in the chemistry of high-spin molecules and single-molecule magnets

The combination of diol-type ligands with paramagnetic transition metal ions has led to the isolation of a host of new homometallic and heterometallic clusters, high-spin molecules and single molecule magnets ranging in nuclearity from two to forty four and with spin ground states as large as S = 61/2. The ligands, whose cluster coordination chemistry is discussed in this article, are 1,3-propanediol and its derivatives, diethanolamine and its derivatives, pyridine-2,6-dimethanol and the gem-diol form of di-2-pyridyl ketone. The structural diversity of the complexes stems from the ability of the ligands to adopt a variety of bridging coordination modes depending on the positions of the two hydroxyl groups in the molecule, the presence/absence of extra donor groups and on the reaction conditions. Examples of 'true' reactivity chemistry involving clusters of diol-type ligands are also given. The activation of pyridine-2,6-dimethanol and di-2-pyridyl ketone by 3d-metal centres towards further reactions seems to be an emergent area of synthetic chemistry.     

Synthetic and structural chemistry of groups 11 and 12 metal complexes of the zwitterionic ammonium thiolate ligands

The chemistry of metal complexes of the zwitterionic ammonium thiolates has expanded dramatically in the recent years. This review is intended to summarize the synthesis and crystal structures of groups 11 and 12 metal zwitterionic ammonium thiolate complexes. Seven methods for the synthesis of these metal complexes of the zwitterionic ammonium thiolates are outlined: proton transfer reaction, precursor reaction, ligand exchange reaction, oxidation–reduction reaction, solid-state reaction, electrochemical reaction and hydro(solvo)thermal reaction. These metal complexes of the zwitterionic ammonium thiolates are classified according to the number of metal atoms; their specific structures are briefly discussed.     

The synthesis, coordination chemistry and ethylene polymerisation activity of ferrocenediyl nitrogen-substituted ligands and their metal complexes

Treatment of aminoferrocene with substituted 2-hydroxybenzaldehydes yields the air- and moisture-stable ligands 1–4, which were then reacted to form the chromium dichloride complexes 5–7 and the nickel bis-chelate species 8 and 9. The metal compounds are very air-sensitive but the chromium compounds act as pre-catalysts for the polymerisation of ethylene. Reaction of 1,1′-bis(amino)ferrocene with similarly substituted 2-hydroxybenzaldehyes or simple benzaldehyde gives the ligands 10–12 and 17, respectively. The X-ray crystal structure of 11 shows the molecule to have non-crystallographic C₂ symmetry and to be linked by C–Hπ interactions between the anthracene rings. Titanium-containing complexes 13–16 can be formed utilising ligands 10–12 and there is a change in geometry within the complexes dependent on the adjacent co-ligands, whilst ligand 17 can be reacted with PdClMe(COD) to form the chelate complex 18. Cyclic voltammetric studies have been carried out on 18 and its oxidised analogue 19, but both complexes are inactive towards ethylene polymerisation.     

Asymmetric synthesis of chiral bisoxazolines and their use as ligands in metal catalysis

Novel C₂- and C₁-symmetric chiral bisoxazolines with a cyclic backbone have been synthesized in an asymmetric manner starting from meso anhydrides. All synthetic steps are easy to perform and lead to the desired products in good overall yields. Preliminary investigations revealed the applicability of these new compounds as ligands in transfer hydrogenations and various metal-catalyzed enantioselective C–C-bond forming reactions such as cyclopropanations and Diels–Alder reactions.     

Design and synthesis of multidentate ligands via metal promoted C-N bond formation processes and their coordination chemistry

This presentation reports some novel examples of organic ring amination reactions via metal mediation. The organic transformations are highly regioselective and can be controlled by the proper selection of the mediator complex. The two isomeric organic ligands viz. HL¹ and HL² were isolated in their pure states by the removal of the metal ions. These were fully characterized. The ligand HL¹ has lowpKa, 8.5. Upon deprotonation, it behaves as a potentialbis chelating N,N,N-donors. The coordination chemistry of the HL¹ ligand involving some 3d-metal ions is described. Two unusual low-spin complexes of manganese(II) and iron(III) are reported. The ferric complex displayed a rhombic EPR while, the corresponding manganese compound showed a complex pattern due to hyperfine coupling. All the complexes displayed large number of redox responses. A brief mention about the future projection of this work is noted.     

Regioselective,Solvent‐ and Metal‐Free Chalcogenation of Imidazo[1,2‐a]pyridines by Employing I2/DMSO as the Catalytic Oxidation System

Highly efficient molecular‐iodine‐catalyzed chalcogenations (S and Se) of imidazo[1,2‐a]pyridines were achieved by using diorganoyl dichalcogenides under solvent‐free conditions. This approach afforded the desired products that had been chalcogenated regioselectively at the C3 position in up to 96 % yield by using DMSO as an oxidant, in the absence of a metal catalyst, and under an inert atmosphere. This mild, green approach allowed the preparation of different types of chalcogenated imidazo[1,2‐a]pyridines with structural diversity. Furthermore, the current protocol was also extended to other N‐heterocyclic cores.     

Sulfur and selenium: the role of oxidation state in protein structure and function

Sulfur and selenium occur in proteins as constituents of the amino acids cysteine, methionine, selenocysteine, and selenomethionine. Recent research underscores that these amino acids are truly exceptional. Their redox activity under physiological conditions allows an amazing variety of posttranslational protein modifications, metal free redox pathways, and unusual chalcogen redox states that increasingly attract the attention of biological chemists. Unlike any other amino acid, the "redox chameleon" cysteine can participate in several distinct redox pathways, including exchange and radical reactions, as well as atom-, electron-, and hydride-transfer reactions. It occurs in various oxidation states in the human body, each of which exhibits distinctive chemical properties (e.g. redox activity, metal binding) and biological activity. The position of selenium in the periodic table between the metals and the nonmetals makes selenoproteins ideal catalysts for many biological redox transformations. It is therefore apparent that the chalcogen amino acids cysteine, methionine, selenocysteine, and selenomethionine exhibit a unique biological chemistry that is the source of exciting research opportunities.