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

Heard, Peter J, Kite, Kenneth, Sogaard Nielson, Julie and Tocher, Derek A (2000) Trimethylplatinum(IV) complexes of dithiocarbamato ligands: an experimental NMR study on the barrier to C-N bond rotation.

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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 were 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 N substituents are discussed. The X-ray structures of fac-[PtMe3(Me2NCS2)]2 (2) and fac-[PtMe3(Ph(H)NCS2)]2 , (6) are reported.

Item Type: Article
Additional Information: Copyright © 2000 RCS, and reproduced here by permission of The Royal Society of Chemistry (RSC).This is the author's final draft after peer review. The article was published in Heard, P. J., Kite, K., Nielsen, J. S., and Tocher, D. A. (2000) 'Trimethylplatinum(IV) complexes of dithiocarbamato ligands: an experimental NMR study on the barrier to C-N bond rotation'. Dalton Transactions, 8, 1349-1356 by the Royal Society of Chemistry and is available online at http://dx.doi.org/10.1039/B000264J
Keywords: Dithiocarbamate complexes, trimethylplatinum(IV), dynamic NMR, restricted rotation
Divisions: ?? GlyndwrUniversity ??
Depositing User: ULCC Admin
Date Deposited: 05 Oct 2011 09:13
Last Modified: 11 Dec 2017 20:05
URI: http://glyndwr.repository.guildhe.ac.uk/id/eprint/141

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