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.

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F03%3A54030062" target="_blank" >RIV/61388955:_____/03:54030062 - isvavai.cz</a>
Result on the web
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DOI - Digital Object Identifier
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Result language
angličtina
Original language name
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.
Original language description
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)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.
Czech name
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Czech description
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Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CF - Physical chemistry and theoretical chemistry
OECD FORD branch
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Project
<a href="/en/project/OC%20D15.10" target="_blank" >OC D15.10: Electrochemistry of nano-structures at heterogeneous interfaces: formation, properties and electron transfer reactions.</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>Z - Vyzkumny zamer (s odkazem do CEZ)

Publication year
2003
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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