Issue 14, 1996

Synthesis, platinum-195 nuclear magnetic resonance spectroscopic and extended X-ray absorption fine structure studies on platinum-(II) and -(IV) thioether macrocyclic complexes

Abstract

Reaction of [PtL][PF6]2(L =[12]aneS4= 1,4,7,10-tetrathiacyclododecane, [14]aneS4= 1,4,8,11-tetrathiacyclotetradecane or [16]aneS4= 1,5,9,13-tetrathiacyclohexadecane) with Cl2–CCl4 or Br2–CCl4 in MeCN solution afforded the corresponding platinum(IV) species [PtX2L][PF6]2 in high yield as yellow (X = Cl) or orange (X = Br) solids. These species have been characterised by IR spectroscopy, FAB mass spectrometry and microanalytical data. Platinum-195 NMR spectroscopic studies on the parent platinum(II) complexes and on the platinum(IV) oxidation products confirm S4 and S4X2 donor sets respectively. These studies also indicate that [PtX2([16]aneS4)][PF6]2 probably exist as trans-dihalides, whereas [PtX2([12]aneS4)][PF6]2 and [PtX2([14]aneS4)][PF6]2 are probably cis-dihalides. The crystal structure of [Pt([16]aneS4)][PF6]2·2MeCN shows the PtII occupying a crystallographic inversion centre, co-ordinated to a square-planar tetrathia donor set with the free S-based lone pairs adopting the up, up, down, down configuration, Pt–S 2.310(2)Å. Platinum L-III edge EXAFS (extended X-ray absorption fine structure) data have been recorded for these complexes. The Pt–S bond lengths for the platinum(II) complexes compare well with those derived from single-crystal X-ray crystallography, while the Pt–S and Pt–X distances determined from EXAFS studies for the platinum(IV) complexes show that oxidation of PtII to PtIV typically results in a slight lengthening of the Pt–S bond lengths.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1996, 2979-2983

Synthesis, platinum-195 nuclear magnetic resonance spectroscopic and extended X-ray absorption fine structure studies on platinum-(II) and -(IV) thioether macrocyclic complexes

A. J. Blake, M. J. Bywater, R. D. Crofts, A. M. Gibson, G. Reid and M. Schröder, J. Chem. Soc., Dalton Trans., 1996, 2979 DOI: 10.1039/DT9960002979

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.

Spotlight

Advertisements