Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 20, 1994
Previous Article Next Article

Mixed phosphathia macrocyclic chemistry: synthesis and characterisation of [M(Ph2[14]ane P2S2)]2+(M = Pd or Pt) and [RhCl2(Ph2[14]ane P2S2)]+(Ph2[14]ane P2S2= 8, 12-diphenyl-1, 5-dithia-8, 12-diphosphacyclotetradecane)

Abstract

The new diphosphadithia macrocycle 8, 12-diphenyl-1, 5-dithia-8, 12-diphosphacyclotetradecane (Ph2[14] ane P2S2) has been prepared and the meso isomer isolated as a white solid. Upon reaction with MCl2(M = Pd or Pt) in the presence of TIPF6in refluxing MeCN this isomer gave [M (Ph2[14]aneP2S2)][PF6]2. The crystal structure of [Pt(Ph2[14]aneP2S2)][PF6]2·MeNO2shows tetradentate P2S2 co-ordination at Pt″ giving a distorted square-planar geometry with Pt–P 2.247(3), 2.252(3)Å and Pt–S 2.343(3), 2.341(4)Å. Phosphorus-31 and 195Pt NMR spectroscopic data confirm retention of this P2S2 co-ordination in solution. Treatment of RhCl3·3H2O with Ph2[14]aneP2S2in refluxing aqueous EtOH followed by addition of an excess of NH4PF6gave [RhCl2(Ph2[14]aneP2S2)]PF6as a yellow solid. The 31P NMR spectrum indicates that the complex exists as the trans-dichloro isomer exclusively, and a single-crystal X-ray structure determination confirms this. The crystal structure of [RhCl2(Ph2[14]aneP2S2)] PF6shows the macrocyclic donor atoms occupying the four equatorial co-ordination sites around the central RhIII ion, Rh–P 2.286(1 ), 2.300(1 )Å, Rh–S 2.374(1), 2.377(1)Å, with trans-dichloro ligands, Rh–Cl 2.347(1), 2.354(1)Å, giving a distorted octahedral geometry. Cyclic voltammetry shows that the complexes [M(Ph2[14]aneP2S2)][PF6]2(M = Pd or Pt) and trans-[RhCl2(Ph2[14]aneP2S2)]PF6each exhibit an irreversible reduction at Epc values of –1.40, –1.93 and –1.06 V vs.ferrocene–ferrocenium respectively.

Back to tab navigation

Article information


J. Chem. Soc., Dalton Trans., 1994, 3031-3037
Article type
Paper

Mixed phosphathia macrocyclic chemistry: synthesis and characterisation of [M(Ph2[14]ane P2S2)]2+(M = Pd or Pt) and [RhCl2(Ph2[14]ane P2S2)]+(Ph2[14]ane P2S2= 8, 12-diphenyl-1, 5-dithia-8, 12-diphosphacyclotetradecane)

N. R. Champness, C. S. Frampton, G. Reid and D. A. Tocher, J. Chem. Soc., Dalton Trans., 1994, 3031
DOI: 10.1039/DT9940003031

Search articles by author

Spotlight

Advertisements