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  • 1
    ISSN: 1434-1948
    Schlagwort(e): Asymmetric catalysis ; Transfer hydrogenation ; Ruthenium ; Amino alcohol ligands ; X-ray structure ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The nature of ruthenium-amino alcohol precursors in the catalytic cycle of asymmetric hydrogen transfer reactions was studied using two C2-symmetrical tetradentate ligands (1 and 2) that were synthesised from (nor)ephedrine. The structure of the catalyst precursor was examined through catalysis and NMR experiments. It was shown that the active catalyst contains one ligand per metal, which coordinates in a didentate N,O fashion (9). In addition, a RuIICl2 complex, in which N,N′-bis(2-hydroxy-1-methyl-2-phenylethyl)-1,2-diaminoethane (1) coordinates through two nitrogen atoms, was structurally characterised by X-ray diffraction (8). - Based on the results of this study a series of new amino alcohol ligands was synthesised from easily available starting materials. Optimisation of the amino alcohol ligand structure resulted in the most effective chiral amino alcohol ligand (5) so far that is capable of reducing acetophenone at 0 °C with up to 97% ee in the RuII-catalysed transfer hydrogenation.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 2
    ISSN: 1434-1948
    Schlagwort(e): Palladium ; Platinum ; Bidentate nitrogen ligands ; p-Quinone ; Alkenes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Compounds of the type M(N∩N-κN)(nq)2 and M2(μ2-N∩N)(μ2-pbq)2, in which nq = 1,4-naphthoquinone, pbq = 1,4-benzoquinone, and N∩N is a monodentate or bridging ligand of the α-diimine type, were obtained from reactions of Pd(dba)2 in toluene with the 3,3′-annelated-2,2′-bipyridines: 4,5-diazafluoren-9-one (dafo) and 4,5-diazafluorene (dafe) in the presence of the appropriate p-quinone. In the corresponding reactions with 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen), 2,2′-bipyrimidine (bpym), N,N′-dicyclohexyl-1,4-diaza-1,3-butadiene (chex-dab), bis[N-(o,o′-diisopropyl)phenylimino]acenaphthene (o,o′-iPr2-bian) and 5,6-dihydro-1,10-phenanthroline (dh-phen) only complexes of the type M(N∩N-κ2N)(Q) were formed (Q = nq, pbq). The structures of the complexes have been established by NMR in solution and by X-ray diffraction in the solid state; crystal structures of Pd(bpy-κ2N)(η2-pbq) (1) Pd(dafo-κN)(η2-nq)2 (14) and Pd2(μ2-dafo)(μ2,η2:η2-pbq)2 (16) have been determined. Of the ligands, dafo and dafe are the only ones apt to form complexes containing a monodentate or bridging N∩N ligand. This behaviour is ascribed to the geometrical constraints of dafo and dafe; the annelation by one carbon atom at the 3,3′-positions in these ligands causes an increase in bite angle from approximately 77° to 82°.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1243-1251 
    ISSN: 1434-1948
    Schlagwort(e): Ruthenium ; α-Diimine ligand ; Carbonylmetal compounds ; Isomers ; X-ray structure ; Resonance Raman spectra ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The syntheses, structures, and spectroscopic properties are reported for trans,cis and cis,cisisomers of [Ru(I)(Me)(CO)2(α-diimine)] [α-diimine = N,N′-diisopropyl-1,4-diazabutadiene (iPr-DAB), pyridine-2-carbaldehyde N-isopropylimine (iPr-PyCa), 4,4′-dimethyl-2,2′-bipyridine (dmb)] which differ in their photochemical behaviour. The structures of trans,cis- and cis,cis-[Ru(I)(Me)(CO)2(iPr-DAB)] have been determined by a single-crystal X-ray diffraction study. The crystals of both isomers are monoclinic and belong to the same P21/n space group with Z = 4. Refinement converged to R = 0.043 for the trans,cis isomer and to R = 0.065 for the cis,cisisomer. Both complexes have a distorted octahedral geometry, in the cis,cisisomer the methyl ligand is located in an equatorial, the iodide in an axial position. According to the 1H- and 13C-NMR and resonance Raman spectra the imine groups of the iPr-DAB ligand are inequivalent in the cis,cis isomer. The absorption spectra vary with the α-diimine, not so much with the isomeric structure of the complex. Both isomers possess two visible absorption bands, which, according to the resonance Raman spectra, belong to charge transfer transitions from mixed metal-halide orbitals to the α-diimine. The resonance Raman spectra show that this charge transfer excitation is accompanied, for both isomers, with an angular distortion of the methyl ligand. These spectral data show that the difference in photochemical behaviour of the two isomers is not due to a change in the excited state character.
    Materialart: Digitale Medien
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  • 4
    ISSN: 1434-1948
    Schlagwort(e): Palladium ; Insertion reactions ; Tridentate ligands ; Hydrazones ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Potentially tridentate hydrazonic ligands of the type HNNO have been used in the synthesis of some methyl palladium(II) complexes. Depending on the applied experimental conditions two different kinds of complexes are obtained. Thus, the reactions between HL1-HL5 and (COD)PdMeCl in diethyl ether led to the formation of bidentate methyl complexes of the type Pd(HNN)MeCl (1-5), where the ligands maintain a neutral character. However, in the presence of a base such as Et3N or NaOMe, the ligands are deprotonated with the consequent formation of tridentate methyl complexes of the type Pd(NNO)Me (7-10). In solution, complexes 1-5 tend to lose the hydrazonic proton with elimination of methane and formation of a tridentate chloride complex Pd(NNO)Cl (6); this tendency can be correlated with the acidity of the free ligands, which has been determined. On bubbling carbon monoxide through solutions of 1-5, the corresponding acetyl complexes Pd(HNN)[C(O)Me]Cl (11-15) are formed, in which both the cis and trans isomers are present. Their molar ratio is rationalised from the results of a molecular modelling study on the basis of electronic considerations. A remarkably different reactivity has been found in the carbonylation of the tridentate complexes 7-10: they decompose rapidly and quantitatively to palladium black and an organic product corresponding to the ligand with an acetyl group bonded to the hydrazonic nitrogen. The X-ray structures of a methyl complex (3) and its corresponding acetyl (13) derivative have been determined.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 5
    ISSN: 1434-1948
    Schlagwort(e): Triosmium cluster ; Biphosphinine ; Crystal structure ; Cyclic voltammetry ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The crystal structure of the novel cluster [Os3(CO)10(4,4′,5,5′-tetramethyl-2,2′-biphosphinine)] reveals an unprecedented coordination mode of the biphosphinine ligand that occupies a doubly-bridging position spanning the open osmium triangle. The cluster is photostable, pointing to a localization of the lowest-energy electronic transition largely on the negatively charged biphosphinine ligand.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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