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.
Disciplines
Chemistry | Inorganic Chemistry | Organic Chemistry | Physical Chemistry
Recommended Citation
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
Digital Commons Citation
Heard, Peter J.; Kite, Kenneth; Sogaard Nielson, Julie; and Tocher, Derek A., "Trimethylplatinum(IV) complexes of dithiocarbamato ligands: an experimental NMR study on the barrier to C-N bond rotation." (2000). Chemistry. Paper 2.
http://epubs.glyndwr.ac.uk/chem/2
Tables
heard Trimethylplatinum(IV) complexes of dithiocarbamato ligands an experimental NMR study on the barrier to C-N bond Figure Legends.doc (22 kB)
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heard Trimethylplatinum(IV) complexes of dithiocarbamato ligands an experimental NMR study on the barrier to C-N bond Figure 1.doc (25 kB)
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heard Trimethylplatinum(IV) complexes of dithiocarbamato ligands an experimental NMR study on the barrier to C-N bond Figure 2 (2).doc (361 kB)
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heard Trimethylplatinum(IV) complexes of dithiocarbamato ligands an experimental NMR study on the barrier to C-N bond Figure 3.doc (71 kB)
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heard Trimethylplatinum(IV) complexes of dithiocarbamato ligands an experimental NMR study on the barrier to C-N bond Figure 4.doc (38 kB)
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heard Trimethylplatinum(IV) complexes of dithiocarbamato ligands an experimental NMR study on the barrier to C-N bond Figure 5.doc (57 kB)
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heard Trimethylplatinum(IV) complexes of dithiocarbamato ligands an experimental NMR study on the barrier to C-N bond Figure 6.doc (58 kB)
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heard Trimethylplatinum(IV) complexes of dithiocarbamato ligands an experimental NMR study on the barrier to C-N bond Figure 7.doc (39 kB)
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heard Trimethylplatinum(IV) complexes of dithiocarbamato ligands an experimental NMR study on the barrier to C-N bond Schemes.doc (25 kB)
Schemes
Comments
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://www.rsc.org