Number of the records: 1  

Aminoallenylidene Complexes of Ruthenium(II) from the Regioselective Addition of Secondary Amines to Butatrienylidene Intermediates: A Combined Experimental and Theoretical Study of the Hindered Rotation around the CN-Bond

  1. 1.
    SYSNO ASEP0181641
    Document TypeJ - Journal Article
    R&D Document TypeJournal Article
    Subsidiary JOstatní články
    TitleAminoallenylidene Complexes of Ruthenium(II) from the Regioselective Addition of Secondary Amines to Butatrienylidene Intermediates: A Combined Experimental and Theoretical Study of the Hindered Rotation around the CN-Bond
    Author(s) Winter, R. F. (DE)
    Hartmann, S. (DE)
    Záliš, Stanislav (UFCH-W) RID, ORCID
    Klinkhammer, K. W. (DE)
    Source TitleJournal of the Chemical Society. Dalton Transactions - ISSN 1472-7773
    - (2003), s. 2342-2352
    Number of pages11 s.
    Languageeng - English
    CountryGB - United Kingdom
    Keywordsaminoallenylidene complexes ; ruthenium ; experimental study
    Subject RIVCF - Physical ; Theoretical Chemistry
    R&D ProjectsOC D15.10 GA MŠMT - Ministry of Education, Youth and Sports (MEYS)
    CEZAV0Z4040901 - UFCH-W
    AnnotationAminoallenylidene complexes trans-[Cl(dppm)2RuC3(NRR'')(CH3)]+ are obtained from the regioselective addition of secondary amines to trans-[Cl(dppm)2Ru=C=C=C=CH2]+. Unsymmetrically substituted amines give rise to Z/E isomeric mixtures. Dynamic 31P-NMR spectroscopy gave an energy barrier of about 85 kJ/mol T for rotation around the CN-bond pointing to a large contribution of the iminium alkynyl resonance form trans-[Cl(dppm)2RuůCC-C(=NRR'''')(CH3)]+. This is also indicated by the pronounced bond length alternation within the RuC3N-chain as is revealed by X-ray structure analysis of the Z isomer of the (benzylmethyl)methylamine derivative 2d. The issue of NR2 rotation was also addressed by DFT calculations on the trans-[Cl(dhpm)2RuC3{N(CH3)2}(CH3)]+ model complex (dhpm = H2PCH2PH2). Upon rotation around the iminium type CN bond nitrogen lone pair and the -system of the allenylidene ligand are decoupled resulting in a significantly longer CN bond.
    WorkplaceJ. Heyrovsky Institute of Physical Chemistry
    ContactMichaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196
    Year of Publishing2004

Number of the records: 1  

  This site uses cookies to make them easier to browse. Learn more about how we use cookies.