Preparative and electrochemical investigations on the electron sponge behavior of cobalt telluride clusters: CO substitution in [Co11Te7(CO)10]n- ions (n=1, 2) by PMe2Ph and crystal structure of [Co11Te7(CO)5(PMe2Ph)5

The reaction of the cluster salts [Cp(2*) Nb(CO)(2)](n)[Co(11)Te(7)(CO)(10)] (Cp*=C(5)Me(5); n=1, 2) with excess PMe(2)Ph gave the neutral, dark brown clusters [Co(11)Te(7)(CO)(6)(PMe(2)Ph)(4)] (5) and [Co(11)Te(7)(CO)(5)(PMe(2)Ph)(5)] (6) with 147 metal valence electrons. The new compounds were characterized by IR spectroscopy, elemental analyses, and mass spectrometry. The molecular structure of 6 was determined by X-ray crystallography. Like its precursor anion, it consists of a pentagonal-prismatic [Co(11)Te(7)] core, but with a ligand sphere composed of five CO and five PMe(2)Ph ligands. Detailed electrochemical studies of both reactions reveal that a stepwise substitution of CO ligands in the initial cluster anions takes place leading to intermediate [Co(11)Te(7)(CO)(10-m)(PMe(2)Ph)(m)](n-) ions (m=1-5; n=1, 2). Each of these intermediates is distinguished by at least one oxidation and two reduction waves, giving rise to a total of 21 redox couples and 27 electroactive species. The electron sponge character of the new compounds is particularly pronounced in 5, which exhibits charges n between +1 and -4 corresponding to metal valence electron counts of between 146 and 151.     

Addition of nitriles to alkaline earth metal complexes of 1,2-bis[(phenyl)imino]acenaphthenes

Compounds [Sr(dpp-bian)(thf)4] (2), [Ba(dpp-bian)(dme)2.5] (3) and [Mg(dtb-bian)(thf)2] (4) (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene; dtb-bian = 1,2-bis[(2,5-di-tert-butylphenyl)imino]acenaphthene) were prepared by reduction of dpp-bian and dtb-bian with an excess of metallic Mg, Sr, or Ba in THF or DME. Reactions of [Mg(dpp-bian)(thf)3], 3, and 4 with diphenylacetonitrile gave keteniminates [Mg(dpp-bianH)(NCCPh2)(thf)2] (5), [Mg(dtb-bianH)(NCCPh2)(thf)2] (6), and [Ba(dpp-bianH)(NCCPh2)(dme)2] (7), respectively. The reaction of 2 with CH3C[triple chemical bond]N in THF gave [{Sr(dpp-bianH)[N(H)C(CH3)C(H)CN](thf)}2] (8). The compounds 2, 3, 5-8 were characterized by elemental analysis, and IR and NMR spectroscopy. Molecular structures of 2, 3, 7, and 8 were determined by single-crystal X-ray diffraction. In contrast to reactions of alkali-metal reagents, magnesium amides, or yttriumalkyls with alpha-H acidic nitriles, which are accompanied by an amine or an alkane elimination, the reactions of [Mg(dpp-bian)(thf)3] (1), 2, 3, and 4 with such nitriles proceeded with formation of Mg, Sr, and Ba keteniminates and simultaneous protonation of one nitrogen atom of the bian ligand. The NMR spectroscopic data obtained for complex 5 indicated that in solution the amino hydrogen atom underwent the fast (on the NMR timescale) shuttle transfer between both nitrogen atoms of the dpp-bianH ligand.     

Chiral Phosphino‐ and (Phosphinooxy)‐Substituted N‐Heterocyclic Carbene Ligands and Their Application in Iridium‐Catalyzed Asymmetric Hydrogenation

Enantiomerically pure iridium complexes with phosphino‐ and (phosphinooxy)‐substituted N‐heterocyclic carbene (NHC) ligands were synthesized. Investigation of their electronic properties showed a similar trans influence of the phosphino (or phosphinooxy) and the NHC units. The complexes were tested in iridium‐catalyzed hydrogenation. While low conversions were observed with unfunctionalized olefins, the catalysts proved to be suitable for hydrogenation of the α,β‐unsaturated ester 20 , allylic alcohol 21 , and imine 22 . The enantioselectivities were, however, moderate.     

An alternative efficient redox couple for the dye-sensitized solar cell system

A series of new cobalt complexes [Co(LLL)(2)X(2)] were synthesized and evaluated as redox mediators for dye-sensitized nanocrystalline TiO(2) solar cells. The structure of the ligand and the nature of the counterions were found to influence the photovoltaic performance. The one-electron-transfer redox mediator [Co(dbbip)(2)](ClO(4))(2) (dbbip = 2,6-bis(1'-butylbenzimidazol-2'-yl)pyridine) performed best among the compounds investigated. Photovoltaic cells incorporating this redox mediator yielded incident photon-to-current conversion efficiencies (IPCE) of up to 80%. The overall yield of light-to-electric power conversion reached 8 % under simulated AM1.5 sunlight at 100 W m(-2) intensity and more than 4% at 1000 W m(-2). Photoelectrodes coated with a 2 microm thick nanoporous layer and a 4 microm thick light-scattering layer, sensitized with a hydrophobic ruthenium dye, gave the best results.     

Understanding the catalytic role of flexible chiral δ-amino alcohols: the 1-(2-aminoethyl)norbornan-2-ol model

An empiric first approach to the knowledge about the structural factors influencing the catalytic behavior of conformationally flexible δ-amino-alcohol-based ligands, for the enantioselective addition of dialkylzincs to prochiral carbonyl groups, has been applied using the 1-(2-aminoethyl)norbornan-2-ol moiety as the model chiral system, and the asymmetrically catalyzed addition of diethylzinc to benzaldehyde as the test reaction. For this purpose, a selected small library of seven norbornane-based chiral ligands, bearing well-defined structural variations to allow a comparative study, that is, variation of the relative configuration and steric hindrance at the C(2), C(3) and/or C(7) norbornane positions, has been synthesized and probed in the mentioned test reaction. The experimental results obtained have been rationalized empirically using diastereomeric Noyori-like transition states, demonstrating that the conformational flexibility of the δ-amino-alcohol ligands, contrary to the more studied and rigid β-amino-alcohols, plays a crucial role on the catalytic behavior of such ligands (stereochemical sense and degree of the stereodifferentiation in the asymmetric process), which makes such structural factors, important for the improved design of new related chiral catalysts. In this sense, a robust crude empirical model for the prediction of the catalytic behavior of such δ-amino-alcohol-based ligands is proposed.     

Siliceous materials with the surface polymer layer composed of dextran-polyimine mixture as column packings for liquid chromatography

Summary Forming a polymer layer on the surface of siliceous materials is one of the methods for protecting the silica skeleton from dissolution in alkaline mobile phases as well as eliminating the negative influence of silanol groups on separated molecules e.g. proteins. Polysaccharides, especially their derivatives bearing amine groups, can play the role of the surface layer. This paper discusses the possibilities of preparing such a layer by cross-linking a dextran-polyimine mixture (rather than the traditionally used DEAE-dextran) deposited on the surface of the solid material. The results presented prove the utility of synthesized materials as supports for affinity ligands in high performance affinity chromatography or as supports for complexed metal ions in ligand-exchange chromatography. The properties of the sorbents with a polymer layer can be changed both by the composition of the cross-linked mixture and by chemical modification.     

Synthesis of N-heterocyclic carbene precursors bearing biphenyl units and their use in ruthenium-catalyzed ring-opening metathesis polymerization

A range of new imidazolium and imidazolinium chlorides bearing biphenyl units on their nitrogen atoms was synthesized. They differed by the electron-withdrawing or -donating nature and the steric bulk of the substituents on their aromatic rings. These various N-heterocyclic carbene (NHC) precursors were combined with the [RuCl₂(p-cymene)]₂ dimer and potassium tert-butoxide to generate the corresponding ruthenium-arene complexes [RuCl₂(p-cymene)(NHC)] in situ. The catalytic activity of these species was investigated in the photoinduced ring-opening metathesis polymerization (ROMP) of cyclooctene. The results obtained confirmed the necessity of blocking the ortho-positions of the phenyl rings in the vicinity of the metal center in order to attain high catalytic efficiencies. They also showed that changing the steric and electronic properties of the substituents on the remote phenyl rings of the biphenyl units had no significant influence on the outcome of the polymerization.     

Fluorinated lignands in HPLC

Summary The chromatographic behaviour of C₆F₅(CH₂)₃SiCl₃, C₆H₅(CH₂)₃SiCl₃, CF₃(CF₂)₇CH₂CH₂SiCl₃ and n-C₁₀H₂₁SiCl₃ as well as the bonding of these ligands to silica is described. Phases with partially fluorinated ligands show entirely different chromatographic characteristics to analogous phases, where hydrogen replaces fluorine. The silica with the pentafluorophenyl-3-n-propyl-C₆F₅(CH₂)₃-ligand has higher k-values and a better selectivity for aromatic hydrocarbons than that with phenyl-3-n-propyl C₆H₅(CH₂)₃-groups, whereas the phase with the fluorinated carbon chain is less useful than the silica modified with n-decyltrichlorosilane n-C₁₀H₂₁SiCl₃. The first effect can be explained by complex formation, and the second may be due to a different contact area between the ligand and the solute. The normal hydrocarbon chains hinder each other sterically and expose many adsorption sites, in contrast the perfluorinated chains are sterically fixed and are the first example of real brushes in HPLC.     

New sulfur-coordinating chiral ligands for the Tsuji—Trost reaction

The use of sulfur-coordinating chiral ligands in the palladium-catalyzed asymmetric Tsuji—Trost reaction is reviewed.     

Access to the structures of fluoromagnesium compounds: synthesis and structural characterization of the β-diketiminato magnesium fluoride [{CH(CMeNAr)2}Mg(μ-F)(THF)]2·toluene

β-Diketiminato magnesium fluoride [{CH(CMeNAr)₂}Mg(μ-F)(THF)]₂·toluene (Ar=2,6-i-Pr₂C₆H₃, 2·toluene) was synthesized. The molecular structure of 2 revealed for the first time, the double fluoro bridge feature between the two magnesium atoms with a typical MgF bond length (average 1.95 Å).