Platinum complexes of 5,6-Dihydroacenaphtho[5,6-cd]-1,2-dichalcogenoles

Callum G. M. Benson, Catherine M. Schofield, Rebecca A. M. Randall, Lucy Wakefield, Fergus R. Knight, Alexandra M. Z. Slawin, J. Derek Woollins*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

10 Citations (Scopus)
2 Downloads (Pure)

Abstract

Six bis(phosphane) platinum complexes bearing dichalcogen acenaphthene ligands have been prepared by metathesis from cis-[PtCl2(PR3)(2)] (R-3 = Ph-3, Ph2Me, PhMe2) and the dilithium salts of the parent 5,6-dihydroacenaphtho[5,6-cd]-1,2-dichalcogenoles (AcenapE(2), L1 E = S, L2 E = Se). For their synthesis, the appropriate disulfide or diselenide species was treated with super hydride [LiBEt3H] to afford the dilithium salt by in situ reduction of the AcenapE(2) E-E bond. Further reaction, by metathetical addition to the cis-platinum precursor afforded the respective platinum(II) complexes [Pt(5,6-AcenapE(2))(PR3)(2)] (R-3 = Ph-3: E = S 1, Se 2; R-3 = Ph2Me: E = S 3, Se 4; R-3 = PhMe2: E = S 5, Se 6). All six complexes have been fully characterised, principally by multinuclear magnetic resonance spectroscopy, IR spectroscopy and MS. The selenium complexes 4 and 6 provide examples of AA'X spin systems, as displayed by their P-31{H-1} NMR spectra. The X-ray structures of L1, L2, 1, 2, 5 and 6 were determined and, where appropriate, the platinum metal geometry, peri-atom displacement, splay angle magnitude, acenaphthene ring torsion angles and E center dot center dot center dot E interactions were analysed. The platinum atoms were found to adopt a distorted square-planar geometry in all four complexes, and the nature of the AcenapE(2) ligand plays little part in the conformation of the substituents bound to the trivalent phosphorus atoms.

Original languageEnglish
Pages (from-to)427-437
Number of pages11
JournalEuropean Journal of Inorganic Chemistry
Volume2013
Issue number3
Early online date26 Nov 2012
DOIs
Publication statusPublished - Jan 2013

Keywords

  • Platinum
  • Chalcogens
  • Metathesis
  • Acenaphthene
  • X-ray structure
  • Coordination complex

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