Platinum Complexes of 5, 6‐Dihydroacenaphtho[5, 6‐cd]‐1, 2‐dichalcogenoles. Issue 3 (26th November 2012)

• Record Type: Journal Article
• Authors: Benson, Callum G. M.; Schofield, Catherine M.; Randall, Rebecca A. M.; Wakefield, Lucy; Knight, Fergus R.; Slawin, Alexandra M. Z.; Woollins, J. Derek
• Is Part Of: European journal of inorganic chemistry. Issue 3(2013)
• Page Start: 427
• Page End: 437
• Publication Date: 2012-11-26
• Subjects: Platinum complexes -- Chalcogens -- Metathesis -- Acenaphthene; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201200967
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: Six bis(phosphane)platinum complexes bearing dichalcogen acenaphthene ligands have been prepared by metathesis from cis ‐[PtCl2 (PR3 )2 ] (R3 = Ph3, Ph2 Me, PhMe2 ) and the dilithium salts of the parent 5, 6‐dihydroacenaphtho[5, 6‐ cd ]‐1, 2‐dichalcogenoles (AcenapE2, L1 E = S, L2 E = Se). For their synthesis, the appropriate disulfide or diselenide species was treated with super hydride [LiBEt3 H] to afford the dilithium salt by in situ reduction of the AcenapE2 E–E bond. Further reaction, by metathetical addition to the cis ‐platinum precursor afforded the respective platinum(II) complexes [Pt(5, 6‐AcenapE2 )(PR3 )2 ] (R3 = Ph3 : E = S1, Se2 ; R3 = Ph2 Me: E = S3, Se4 ; R3 = PhMe2 : E = S5, Se6 ). All six complexes have been fully characterised, principally by multinuclear magnetic resonance spectroscopy, IR spectroscopy and MS. The selenium complexes4 and6 provide examples of AA′X spin systems, as displayed by their 31 P{ 1 H} NMR spectra. The X‐ray structures ofL1, L2, 1, 2, 5 and6 were determined and, where appropriate, the platinum metal geometry, peri ‐atom displacement, splay angle magnitude, acenaphthene ring torsion angles and E··· 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 AcenapE2 ligand plays little part in the conformation of the substituents bound to the trivalent phosphorus atoms. Abstract : Six bis(phosphane)platinum complexes bearing 5, 6‐dihydroacenaphtho[5, 6‐ cd ]‐1, 2‐dichalcogenoles (AcenapE2, E = S, Se) have been prepared. They were formed from the metathetical addition of the dilithium precursors to cis ‐[PtCl2 (PR3 )2 ] (R3 = Ph3, Ph2 Me, PhMe2 ).