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  • 1
    ISSN: 1434-1948
    Keywords: Triosmium cluster ; Biphosphinine ; Crystal structure ; Cyclic voltammetry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1434-1948
    Keywords: Palladium ; Platinum ; Bidentate nitrogen ligands ; p-Quinone ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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°.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1243-1251 
    ISSN: 1434-1948
    Keywords: Ruthenium ; α-Diimine ligand ; Carbonylmetal compounds ; Isomers ; X-ray structure ; Resonance Raman spectra ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Type of Medium: Electronic Resource
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