Issue 8, 2000
From the journal:

Journal of the Chemical Society, Dalton Transactions

Trimethylplatinum(IV) complexes of dithiocarbamato ligands: an experimental NMR study on the barrier to C–N bond rotation

Peter J. Heard,*a   Kenneth Kite,b   Julie Søgaard Nielsena  and  Derek A. Tocherc  

* Corresponding authors

a School of Biological and Chemical Sciences, Birkbeck University of London, Gordon House, 29 Gordon Square, London, UK
E-mail: p.heard@chem.bbk.ac.uk

b Department of Chemistry, University of Exeter, Exeter, UK

c Department of Chemistry, University College London, Christopher Ingold Laboratories, 20 Gordon Street, London, UK

Abstract

The trimethylplatinum(IV) complexes of a number of dithiocarbamato ligands have been prepared. The complexes are dimeric in the solid state and in solution, with the ligands acting in both a bridging and chelating fashion. Restricted rotation about the ligand C–N bonds in solution leads to the formation of four rotomers. The kinetics of the restricted rotation was measured by a variety of dynamic NMR techniques in the slow and intermediate exchange regimes. Two distinct processes are observed, namely the independent rotation about each C–N bond and correlated rotation about both C–N bonds. The free energies of activation, which are strongly dependent on the nature of the ligand substituents, are in the range 65–88 kJ mol−1 at 298 K. The origins of the barrier to rotation and the effects of the nitrogen substituents are discussed. The crystal structures of fac-[PtMe3(Me2NCS2)]2 and fac-[PtMe3(Ph(H)NCS2)]2 are reported.

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Article information

DOI
https://doi.org/10.1039/B000264J
Article type
Paper
Submitted
12 Jan 2000
Accepted
08 Mar 2000
First published
30 Mar 2000

J. Chem. Soc., Dalton Trans., 2000, 1349-1356

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Trimethylplatinum(IV) complexes of dithiocarbamato ligands: an experimental NMR study on the barrier to C–N bond rotation

P. J. Heard, K. Kite, J. S. Nielsen and D. A. Tocher, J. Chem. Soc., Dalton Trans., 2000, 1349 DOI: 10.1039/B000264J

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