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.
SYSNO ASEP 0181641 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Ostatní články Title 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 Author(s) Winter, R. F. (DE)
Hartmann, S. (DE)
Záliš, Stanislav (UFCH-W) RID, ORCID
Klinkhammer, K. W. (DE)Source Title Journal of the Chemical Society. Dalton Transactions - ISSN 1472-7773
- (2003), s. 2342-2352Number of pages 11 s. Language eng - English Country GB - United Kingdom Keywords aminoallenylidene complexes ; ruthenium ; experimental study Subject RIV CF - Physical ; Theoretical Chemistry R&D Projects OC D15.10 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) CEZ AV0Z4040901 - UFCH-W Annotation Aminoallenylidene 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)2RuůCC-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. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2004
Number of the records: 1