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Klaus Wurst

Publications and source records attributed to Klaus Wurst.

32 records · Page 2Linked to original sources
PubMed2004

1,3-dialkyl- and 1,3-diaryl-3,4,5,6-tetrahydropyrimidin-2-ylidene rhodium(i) and palladium(II) complexes: synthesis, structure, and reactivity.

The synthesis of novel 1,3-diaryl- and 1,3-dialkylpyrimidin-2-ylidene-based N-heterocyclic carbenes (NHCs) and their rhodium(i) and palladium(II) complexes is described. The rhodium compounds bromo(cod)[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (7), bromo(cod)(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (8) (cod=eta(4)-1,5-cyclooctadiene, mesityl=2,4,6-trimethylphenyl), chloro(cod)(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (9), and chloro(cod)[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (10) were prepared by reaction of [[Rh(cod)Cl](2)] with lithium tert-butoxide followed by addition of 1,3-dimesityl-3,4,5,6-tetrahydropyrimidinium bromide (3), 1,3-dimesityl-3,4,5,6-tetrahydropyrimidinium tetrafluoroborate (4), 1,3-di-2-propyl-3,4,5,6-tetrahydropyrimidinium bromide (6), and 1,3-di-2-propyl-3,4,5,6-tetrahydropyrimidinium tetrafluoroborate, respectively. Complex 7 crystallizes in the monoclinic space group P2(1)/n, and 8 in the monoclinic space group P2(1). Complexes 9 and 10 were used for the synthesis of the corresponding dicarbonyl complexes dicarbonylchloro(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)rhodium (11), and dicarbonylchloro[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene]rhodium (12). The wavenumbers nu(CO I)/nu(CO II) for 11 and 12 were used as a quantitative measure for the basicity of the NHC ligand. The values of 2062/1976 and 2063/1982 cm(-1), respectively, indicate that the new NHCs are among the most basic cyclic ligands reported so far. Compounds 3 and 6 were additionally converted to the corresponding cationic silver(i) bis-NHC complexes [Ag(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)(2)]AgBr(2) (13) and [Ag[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene](2)]AgBr(2) (14), which were subsequently used in transmetalation reactions for the synthesis of the corresponding palladium(II) complexes Pd(1,3-dimesityl-3,4,5,6-tetrahydropyrimidin-2-ylidene)(2) (2+)(Ag(2)Br(2)Cl(4) (4-))(1/2) (15) and Pd[1,3-bis(2-propyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene)(2)]Cl(2) (16). Complex 15 crystallizes in the monoclinic space group P2(1)/c, and 16 in the monoclinic space group C(2)/c. The catalytic activity of 15 and 16 in Heck-type reactions was studied in detail. Both compounds are highly active in the coupling of aliphatic and aromatic vinyl compounds with aryl bromides and chlorides with turnover numbers (TONs) up to 2000000. Stabilities of 15 and 16 under Heck-couplings conditions were correlated with their molecular structure. Finally, selected kinetic data for these couplings are presented.

Journal Article↗
PubMed2004

Synthesis and reactivity of homogeneous and heterogeneous ruthenium-based metathesis catalysts containing electron-withdrawing ligands.

The synthesis and heterogenization of new Grubbs-Hoveyda type metathesis catalysts by chlorine exchange is described. Substitution of one or two chlorine ligands with trifluoroacetate and trifluoromethanesulfonate was accomplished by reaction of [RuCl(2)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (IMesH(2) = 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) with the silver salts CF(3)COOAg and CF(3)SO(3)Ag, respectively. The resulting compounds, [Ru(CF(3)SO(3))(2)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (1), [RuCl(CF(3)SO(3))([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (2), and [Ru(CF(3)CO(2))(2)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (3) were found to be highly active catalysts for ring-closing metathesis (RCM) at elevated temperature (45 degrees C), exceeding known ruthenium-based catalysts in catalytic activity. Turn-over numbers (TONs) up to 1800 were achieved in RCM. Excellent yields were also achieved in enyne metathesis and ring-opening cross metathesis using norborn-5-ene and 7-oxanorborn-5-ene-derivatives. Even more important, 3 was found to be highly active in RCM at room temperature (20 degrees C), allowing TONs up to 1400. Heterogeneous catalysts were synthesized by immobilizing [RuCl(2)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] on a perfluoroglutaric acid derivatized polystyrene-divinylbenzene (PS-DVB) support (silver form). The resulting supported catalyst [RuCl(polymer-CH(2)-O- CO-CF(2)-CF(2)-CF(2)-COO)([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (5) showed significantly reduced activities in RCM (TONs = 380) compared with the heterogeneous analogue of 3. The immobilized catalyst, [Ru(polymer-CH(2)-O-CO-CF(2)-CF(2)-CF(2)-COO)(CF(3)CO(2))([double bond]CH-o-iPr-O-C(6)H(4))(IMesH(2))] (4) was obtained by substitution of both Cl ligands of the parent Grubbs-Hoveyda catalyst by addition of CF(3)COOAg to 5. Compound 4 can be prepared in high loadings (160 mg catalyst g(-1) PS-DVB) and possesses excellent activity in RCM with TONs up to 1100 in stirred-batch RCM experiments. Leaching of ruthenium into the reaction mixture was unprecedentedly low, resulting in a ruthenium content <70 ppb (ng g(-1)) in the final RCM-derived products.

Journal Article↗
PubMed2004

Supramolecular photomagnetic materials: photoinduced dimerization of ferrocene-based polychlorotriphenylmethyl radicals.

New ferrocenyl Schiff-base polychlorotriphenylmethyl radicals have been synthesized and characterized. The imino group of one such radical undergoes an irreversible trans to cis structural isomerization induced by light. Such photoinduced isomerization has been monitored by UV/Vis and ESR spectroscopy and also monitored by HPLC. ESR frozen solution experiments at low temperature revealed that the cis isomer dimerizes, showing a strong antiferromagnetic interaction. Although numerous photochromic supramolecular systems have been described, such a photoinduced self-assembly process represents the first example of a one-way photoswitchable magnetic system in which a conversion between a doublet and a singlet ground state species is promoted by a photoinduced dimerization process driven by the formation of hydrogen bonds. DFT calculations on the minimized structure and on the rotational barriers have been performed to establish the origin of such behavior. The effect of the substituents and the media polarity on the photoisomerization of this imine chromophore have also been studied. It has been observed that the efficiency of the process is markedly dependent on the presence and characteristics of electron-donor and electron-acceptor substituents of the ferrocenyl Schiff-base polychlorotriphenylmethyl radicals as well as on the polarity of the solvent.

Journal Article↗
PubMed2004

Electrochemical synthesis and X-ray crystal structures of beta-D-2-phenylselenyl-1,3,4,6-tetra-O-acetylglucopyranose and alpha-D-2-phenylselenyl-1,3,4,6-tetra-O-acetylmannopyranose.

Electrochemical acetoxyphenylselenation of 3,4-dihydro-2H-pyran and D-3,4,6-tri-O-acetylglucal was studied. The constant current electrolysis (50mA) of dihydropyran and diphenyl diselenide in an acetic acid solution of tetramethylammonium chloride was performed at room temperature in an undivided cell using a graphite anode and an aluminum cathode and yielded trans-DL-2-acetoxy-3-phenylselenyltetrahydropyran (27%), in agreement with Markovnikov's rule. The analysis of the 1H NMR spectral data showed that the acetoxy and phenylselenyl groups adopt axial positions in the most stable conformation of this compound due to the anomeric effect. Under the same conditions D-3,4,6-tri-O-acetylglucal afforded D-2-phenylselenyl-1,3,4,6-tetra-O-acetylglucopyranose and D-2-phenylselenyl-1,3,4,6-tetra-O-acetylmannopyranose, which were separated by column chromatography and isolated in 87% overall yield (isomer ratio 60:40). The structures of these compounds were established by spectral data. Single crystal X-ray structure determinations of the diastereomers are reported.

Crystallography, X-Ray↗
PubMed2003

Solvatochromism, halochromism, and preferential solvation of new dipolar guaiazulenyl 1,4-benzoquinone methides.

The synthesis and the solvatochromic properties of five dyes, obtained by condensation of guaiazulene with 4-hydroxybenzaldehydes, are described. Crystal structures of a quinoid dye and a phenolic dye precursor are presented. The dyes are sensitive to the dipolarity-polarizability of the medium and to the hydrogen-bond donor ability of protic solvents. Their solvatochromism is discussed in terms of Kamlet-Taft's pi* and alpha scales, and their difference in behaviour is interpreted. Alkali and alkaline earth metal salts effect halochromism, with one exception due to extreme steric hindrance. Thus, this dye is capable of measuring solvent polarities without sensing the presence of electrolytes. Preferential solvation of the dyes in a series of binary solvent mixtures is explained quantitatively by solvent-exchange models.

Journal Article↗
PubMed2003

Multistability in a BEDT-TTF based molecular conductor.

The low dimensional organic conductor (BEDT-TTF)(2)Br(1.3)I(1.1)Cl(0.6) [BEDT-TTF = bis(ethylenedithio)tertathiafulvalene] is shown to be a unique molecular solid that exists in three crystalline polymorphic forms (alpha'-, alpha' "-, beta' '-phase) and, surprisingly, is able to adopt the same metal-like beta' '-phase at both low (T < 185 K) and high (T > 395 K) temperatures. Several crystals of the alpha'- and alpha' "-phases have been studied using three different techniques: dc-conductivity measurements, ESR spectroscopy, and X-ray diffraction analysis. All these techniques show the existence of the reversible semiconductor <--> metal (alpha' " <--> beta' ') phase transition at both high and low temperatures as well as the alpha' <--> alpha' " phase transition at high temperatures. The phase transitions of these polymorphs are characterized by huge hysteresis and dramatic changes in the transport and magnetic properties. Based on ab initio calculations, it is suggested that dipole-dipole interactions can play a key role in the rich polymorphism of this molecular solid.

Journal Article↗
PubMed2003

A nanoporous molecular magnet with reversible solvent-induced mechanical and magnetic properties.

Interest in metal-organic open-framework structures has increased enormously in the past few years because of the potential benefits of using crystal engineering techniques to yield nanoporous materials with predictable structures and interesting properties. Here we report a new efficient methodology for the preparation of metal-organic open-framework magnetic structures based on the use of a persistent organic free radical (PTMTC), functionalized with three carboxylic groups. Using this approach, we create an open-framework structure Cu3(PTMTC)2(py)6(CH3CH2OH)2(H2O), which we call MOROF-1, combining very large pores (2.8-3.1 nm) with bulk magnetic ordering. MOROF-1 shows a reversible and highly selective solvent-induced 'shrinking-breathing' process involving large volume changes (25-35%) that strongly influence the magnetic properties of the material. This magnetic sponge-like behaviour could be the first stage of a new route towards magnetic solvent sensors.

Copper↗
PubMed2002

Radical para-benzoic acid derivatives: transmission of ferromagnetic interactions through hydrogen bonds at long distances.

Investigation of the transmission of magnetic interactions through hydrogen bonds has been carried out for two different benzoic acid derivatives which bear either a tert-butyl nitroxide (NOA) or a poly(chloro)triphenylmethyl (PTMA) radical moiety. In the solid state, both radical acids formed dimer aggregates by the complementary association of two carboxylic groups though hydrogen bonding. This association ensured that atoms with most spin density are separated from one another by more than 15 A. Thus, no competing through-space magnetic exchange interactions are expected in these dimers and, hence, they provide good models to investigate whether noncovalent hydrogen bonds play a role in the long-range transmission of magnetic interactions. The nature of the magnetic exchange interaction and their strengths within similar dimer aggregates in solution was assessed by electron spin resonance (ESR) spectroscopy. In the case of radical NOA, low-temperature ESR experiments showed a weak ferromagnetic interaction between the two radicals in the dimer aggregates (which have the same geometry as in the solid state). In contrast, the corresponding solution ESR study performed with radical PTMA did not lead to any conclusive results, as aggregates were formed by noncovalent interactions other than hydrogen bonds. However, the bulkiness of the poly(chloro)triphenylmethyl radical prevented interdimer contacts in the solid state between regions of high spin density. Hence, solid-state measurements of the alpha phase of PTMA radical provided evidence of the intradimer interaction to confirm the transmission of a weak ferromagnetic interaction through the carboxylic acid bridges, as found for the NOA radical. Moreover, crystallization of the PTMA radical in presence of ethanol to form the beta phase of PTMA radical prevented the dimer formation; this resulted in the suppression of this interaction and provides further evidence of the magnetic exchange mechanism through noncovalent hydrogen bonds at long distances.

Journal Article↗
PubMed2001

A New Photomagnetic Molecular System Based on Photoinduced Self-Assembly of Radicals This work was supported by grants from DGI (project MAT 2000-1388-C03-01), CIRIT (project 2000 SGR00114), the 3MD Network of the TMR program of the EU (contract ERBFMRX CT980181), and the ESF program Molecular Magnets. D.R.-M. thanks the Generalitat de Catalunya for a postdoctoral grant, and I.R. thanks the CSIC-Carburos Metálicos and ESF for fellowships.

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Journal Article↗