Klaus Beckerle

Discrimination of cryptochirality in chiral isotactic polystyrene by asymmetric autocatalysis.

Cryptochiral isotactic polystyrene induces the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde, affording the enantioenriched pyrimidyl alkanol with the corresponding absolute configuration to that of polystyrenes in conjunction with asymmetric autocatalysis.

Discrete magnesium hydride aggregates: a cationic Mg13H18 cluster stabilized by NNNN-type macrocycles.

Large magnesium hydride aggregates [Mg13 (Me3 TACD)6 (μ2 -H12 )(μ3 -H6 )][A]2 ((Me3 TACD)H=1,4,7-trimethyl-1,4,7,10-tetraazacyclododecane; A=AlEt4 , AlnBu4 , B{3,5-(CF3 )2 C6 H3 }4 ) were synthesized stepwise from alkyl complexes [Mg2 (Me3 TACD)R3 ] (R=Et, nBu) and phenylsilane in the presence of additional Mg(II) ions. The central magnesium atom is octahedrally coordinated by six hydrides as in solid α-MgH2 of the rutile type. Further coordination to six magnesium atoms leads to a substructure of seven edge-sharing octahedra as found in the hexagonal layer of brucite (Mg(OH)2 ). Upon protonolysis in the presence of 1,2-dimethoxyethane (DME), this cluster was degraded into a tetranuclear dication [Mg2 (Me3 TACD)(μ-H)2 (DME)]2 [A]2 .

Group 3 and 4 metal alkyl and hydrido complexes containing a linked amido-cyclopentadienyl ligand: constrained geometry polymerization catalysts for nonpolar and polar monomers

Abstract In order to understand the nature of the putative cationic 12-electron species [M(η 5 :η 1 -C 5 R 4 SiMe 2 NR′)R″] + of titanium catalysts supported by a linked amido-cyclopentadienyl ligand, several derivatives with different cyclopentadienyl C 5 R 4 and amido substituents R′ were studied systematically. The use of tridentate variants (C 5 R 4 SiMe 2 NCH 2 CH 2 X) 2− (C 5 R 4 =C 5 Me 4 , C 5 H 4 , C 5 H 3 t Bu ; X=OMe, SMe, NMe 2 ) allowed the NMR spectroscopic observation of the titanium benzyl cations [Ti(η 5 :η 1 -C 5 Me 4 SiMe 2 NCH 2 CH 2 X)(CH 2 Ph)] + . Isoelectronic neutral rare earth metal complexes [Ln(η 5 :η 1 -C 5 R 4 SiMe 2 NR′)R″] can be expected to be active for polymerization. To arrive at neutral 12-electron hydride and alkyl species of the rare earth metals, we employed a lanthanide tris(alkyl) complex [Ln(CH 2 SiMe 3 ) 3 (THF) 2 ] (Ln=Y, Lu, Yb, Er, Tb), which allows the facile synthesis of the linked amido-cyclopentadienyl complex [Ln(η 5 :η 1 -C 5 Me 4 SiMe 2 NCMe 3 )(CH 2 SiMe 3 )(THF)]. Hydrogenolysis of the linked amido-cyclopentadienyl alkyl complex leads to the dimeric hydrido complex [Ln(η 5 :η 1 -C 5 Me 4 SiMe 2 NCMe 3 )(THF)(μ-H)] 2 . These complexes are single-site, single-component catalysts for the polymerization of ethylene and a variety of polar monomers such as acrylates and acrylonitrile. Nonpolar monomers such as α-olefins and styrene, in contrast, give isolable mono-insertion products which allow detailed studies of the initiation process.

Supported Molybdenum Catalysts for the Deoxydehydration of 1,4-Anhydroerythritol into 2,5-Dihydrofuran

Efficient deoxygenation strategies are crucial for the valorization of renewable feedstocks. Deoxydehydration (DODH) enables the direct transformation of two adjacent hydroxyl groups into a double bond. Supported molybdenum-based catalysts were utilized for the first time in DODH. MoOx /TiO2 showed superior catalytic activity compared to common molybdenum salts. The catalyst efficiently converted 1,4-anhydroerythritol into 2,5-dihydrofuran in the presence of 3-octanol as reducing agent, showing high reproducibility and stability.

Rare earth metal-based catalysts for the polymerization of nonpolar and polar monomers

The synthesis of rare earth metal half-sandwich hydrido complexes [Ln (h5:h1-C5Me 4SiMe2NCMe3) (THF) (µ-H) ] 2 (Ln = Y, Lu) through s-bond metathesis of the easily accessible alkyl complexes [Ln (h5:h1-C5Me 4SiMe2NCMe3) (CH2 SiMe3) (THF) ] was developed. The dimeric yttrium hydrido complexes are highly fluxional, and a monomer-dimer equilibrium is present. They were tested as single-site, single-component catalysts for the polymerization of ethylene and styrene, as well as alkyl acrylate and acrylonitrile. The hydrido complexes polymerize ethylene slowly and form isolable mono (insertion) products with styrene. The yttrium n-alkyl complexes [Y (h5:h1-C5Me 4SiMe2NCMe3) (R) (THF) ] [R = (CH2) nCH3, n = 3-9], prepared by the mono (insertion) of a-olefins, initiate polymerization in a relatively controlled manner. Thus, styrene was polymerized by the n-alkyl complex to give atactic polystyrenes with somewhat enriched syndiotacticities.

Artificial Diels–Alderase based on the transmembrane protein FhuA

Summary Copper(I) and copper(II) complexes were covalently linked to an engineered variant of the transmembrane protein Ferric hydroxamate uptake protein component A (FhuA ΔCVFtev). Copper(I) was incorporated using an N-heterocyclic carbene (NHC) ligand equipped with a maleimide group on the side arm at the imidazole nitrogen. Copper(II) was attached by coordination to a terpyridyl ligand. The spacer length was varied in the back of the ligand framework. These biohybrid catalysts were shown to be active in the Diels–Alder reaction of a chalcone derivative with cyclopentadiene to preferentially give the endo product.

Towards chiral polystyrene based materials: controlled polymerization of p-(2,2′-diphenylethyl)styrene

p-(2,2′-Diphenylethyl)styrene (DPES) was polymerized in an atactic, syndiotactic, and isospecific fashion. Atactic polymerization was initiated by 2,2′-azobis(2-methylpropionitrile) (AIBN). Syndiotactic polymer was obtained using the catalyst system TiCp*Cl3/MAO. Isospecific polymerization was performed with the homochiral postmetallocene catalyst dichloro{trans-1,2-dithiocyclohexanediyl-2,2′-bis(4,6-di-tert-butylphenolato)}titanium/MAO. Optically active isotactic polymers were obtained by a controlled reduction of the molecular weight, employing two different chain transfer methodologies. In addition to 1-hexene as a chain transfer agent (CTA), the use of diethylzinc as a CTA for DPES oligomerization was introduced. Polymers with molecular weights below Mn of 50,000 g mol−1 showed specific rotation values ([α]23D) between ±0.2 and 2.2.

Layer-by-layer assembly of partially sulfonated isotactic polystyrene with poly(vinylamine).

The stereoregular synthetic polymer isotactic polystyrene bearing partially sulfonated groups (SiPS) was used as a layer-by-layer assembled thin film for the first time. When a low molecular weight compound was employed as the pair for the alternative layer-by-layer (LbL) assembly, the frequency shift was very small using quartz crystal microbalance (QCM) analysis, whereas poly(vinylamine) (PVAm) formed an effective pair for the construction of LbL films with SiPS. When it was neutralized, SiPS was not assembled, probably due to the loss of effective polymer-polymer interactions. The ionic strength conditions revealed a slight difference of the assembly behavior on the isotactic polymer as compared to the atactic one. The assembled LbL film showed the same peaks over the range from 1141 to 1227 cm(-1) and 700 cm(-1) in the FT-IR/ATR spectra as the bulk complex of SiPS/PVAm, and the thickness on one side was calculated at 76 nm by QCM analysis. The surface roughness of the film was also observed by AFM.

2-Methyl-2,4-pentanediol (MPD) boosts as detergent-substitute the performance of ß-barrel hybrid catalyst for phenylacetylene polymerization

Covering hydrophobic regions with stabilization agents to solubilize purified transmembrane proteins is crucial for their application in aqueous media. The small molecule 2-methyl-2,4-pentanediol (MPD) was used to stabilize the transmembrane protein Ferric hydroxamate uptake protein component A (FhuA) utilized as host for the construction of a rhodium-based biohybrid catalyst. Unlike commonly used detergents such as sodium dodecyl sulfate or polyethylene polyethyleneglycol, MPD does not form micelles in solution. Molecular dynamics simulations revealed the effect and position of stabilizing MPD molecules. The advantage of the amphiphilic MPD over micelle-forming detergents is demonstrated in the polymerization of phenylacetylene, showing a ten-fold increase in yield and increased molecular weights.

Rare Earth Half-Sandwich Catalysts for the Homo- and Copolymerization of Ethylene and Styrene

The synthesis of rare earth metal half-sandwich hydrido complexes [Ln(η5:η1-C5Me4SiMe2NCMe3)(THF)(μ-H)]2(Ln = Y, Lu, Yb, Er, Tb) through σ-bond metathesis of the alkyl complexes [Ln(η5:η1- C5Me4SiMe2NCMe3)(CH2SiMe3)(THF)], easily accessible by the reaction of the amino-cyclopentadiene with [Ln(CH2SiMe3)3(THF)2], was developed. The dimeric lanthanide hydrido complexes are highly fluxional involving THF dissociation and cis-trans isomerization of the linked amidocyclopentadienyl ligand. The presence of a monomer-dimer equilibrium is suggested by cross-over experiments. They were tested as single-site, single-component catalysts for the polymerization of ethylene, α-olefin, and styrene, as well as alkyl acrylate and acrylonitrile. The hydrido complexes polymerize ethylene slowly, whereas they form isolable mono(insertion) products with α-olefins and with styrene. The yttrium n-alkyl complexes [Y(η5:η1,-C5Me4SiMe2NCMe3)(R)(THF)n] (R = (CH2)nCH3, n = 3-9), prepared by the mono(insertion) of α-olefins, initiate polymerization of styrene in a relatively controlled manner. Thus, styrene was polymerized by the in-situ formed n-hexyl complex to give atactic polystyrenes with narrow molecular weight distributions and somewhat enriched syndiotacticities. Sequential addition of terf-butyl acrylate allows the synthesis of poly(styrene-block- tert-butyl acrylate).