Publikation: 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
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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 1 for rotation around the CN-bond pointing to a large contribution of the iminium alkynyl resonance form trans-[Cl(dppm)2Ru–C 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, the nitrogen lone pair and the π-system of the allenylidene ligand are decoupled, resulting in a significantly longer CN bond and a tetrahedrally coordinated nitrogen atom.
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WINTER, Rainer F., Stephan HARTMANN, Stanislav ZÁLIS, Karl Wilhelm KLINKHAMMER, 2003. 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. In: Dalton Transactions. 2003(11), pp. 2342-2352. ISSN 1477-9226. Available under: doi: 10.1039/B211774FBibTex
@article{Winter2003Amino-13835, year={2003}, doi={10.1039/B211774F}, 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}, number={11}, issn={1477-9226}, journal={Dalton Transactions}, pages={2342--2352}, author={Winter, Rainer F. and Hartmann, Stephan and Zális, Stanislav and Klinkhammer, Karl Wilhelm}, note={Supplemental material: http://www.rsc.org/suppdata/dt/b2/b211774f/} }
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