Issue 11, 2003
From the journal:

Dalton Transactions

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†

Rainer F. Winter,a   Stephan Hartmann,a   Stanislav Zálišb  and  Karl Wilhelm Klinkhammerc  

a Institut für Anorganische Chemie der Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany
E-mail: winter@iac.uni-stuttgart.de

b J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejškova 3, Prague, Czech Republic
E-mail: stanislav.zalis@jh-inst.cas.cz

c Institut für Anorganische Chemie, Johannes-Gutenberg-Universität Mainz, Duesbergweg 10-14, D-55099 Mainz, Germany
E-mail: klink@uni-mainz.de

Abstract

Aminoallenylidene complexes trans-[Cl(dppm)2RuC3(NRR′)(CH3)]+ are obtained from the regioselective addition of secondary amines to trans-[Cl(dppm)2Ru[double bond, length as m-dash]C[double bond, length as m-dash]C[double bond, length as m-dash]C[double bond, length as m-dash]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[triple bond, length as m-dash]C–C([double bond, length as m-dash]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.

Graphical abstract: 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

About
Cited by
Related
Download options Please wait...

Supplementary files

Article information

DOI
https://doi.org/10.1039/B211774F
Article type
Paper
Submitted
28 Nov 2002
Accepted
14 Apr 2003
First published
29 Apr 2003

Dalton Trans., 2003, 2342-2352

Permissions

Request permissions

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

R. F. Winter, S. Hartmann, S. Záliš and K. Wilhelm Klinkhammer, Dalton Trans., 2003, 2342 DOI: 10.1039/B211774F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements