title: Synthesis, characterisation and photochemistry of Pt(IV) pyridyl azido acetato complexes.
abstract: Pt(II) azido complexes [Pt(bpy)(N(3))(2)] (1), [Pt(phen)(N(3))(2)] (2) and trans-[Pt(N(3))(2)(py)(2)] (3) incorporating the bidentate diimine ligands 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen) or the monodentate pyridine (py) respectively, have been synthesised from their chlorido precursors and characterised by X-ray crystallography; complex 3 shows significant deviation from square-planar geometry (N(3)-Pt-N(3) angle 146.7 degrees ) as a result of steric congestion at the Pt centre. The novel Pt(IV) complexes trans, cis-[Pt(bpy)(OAc)(2)(N(3))(2)] (), trans, cis-[Pt(phen)(OAc)(2)(N(3))(2)] (), trans, trans, trans-[Pt(OAc)(2)(N(3))(2)(py)(2)] (), were obtained from via oxidation with H(2)O(2) in acetic acid followed by reaction of the intermediate with acetic anhydride. Complexes 4-6 exhibit interesting structural and photochemical properties that were studied by X-ray, NMR and UV-vis spectroscopy and TD-DFT (time-dependent density functional theory). These Pt(IV) complexes exhibit greater absorption at longer wavelengths (epsilon = 9756 M(-1) cm(-1) at 315 nm for 4 ; epsilon = 796 M(-1) cm(-1) at 352 nm for 5 ; epsilon = 16900 M(-1) cm(-1) at 307 nm for 6 , in aqueous solution) than previously reported Pt(IV) azide complexes, due to the presence of aromatic amines, and 4-6 undergo photoactivation with both UVA (365 nm) and visible green light (514 nm). The UV-vis spectra of complexes 4-6 were calculated using TD-DFT; the nature of the transitions contributing to the UV-vis bands provide insight into the mechanism of production of the observed photoproducts. The UV-vis spectra of 1-3 were also simulated by computational methods and comparison between Pt(II) and Pt(IV) electronic and structural properties allowed further elucidation of the photochemistry of 4-6.
authors.affiliation: School of Chemistry, University of Edinburgh, West Mains Road, Edinburgh, UKEH9 3JJ.
authors.forename: Fiona S
authors.initials: FS
authors.lastname: Mackay
authors.forename: Nicola J
authors.initials: NJ
authors.lastname: Farrer
authors.forename: Luca
authors.initials: L
authors.lastname: Salassa
authors.forename: Hui-Chung
authors.initials: HC
authors.lastname: Tai
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Deeth
authors.forename: Stephen A
authors.initials: SA
authors.lastname: Moggach
authors.forename: Peter A
authors.initials: PA
authors.lastname: Wood
authors.forename: Simon
authors.initials: S
authors.lastname: Parsons
authors.forename: Peter J
authors.initials: PJ
authors.lastname: Sadler
mesh_terms: D000085:Acetates / Q000737:chemistry*; D001386:Azides / Q000737:chemistry*; D003198:Computer Simulation; D018360:Crystallography, X-Ray; D008024:Ligands; D008956:Models, Chemical; D008958:Models, Molecular; D009944:Organoplatinum Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010777:Photochemistry; D011725:Pyridines / Q000737:chemistry*
chemical_list: D000085:Acetates; D001386:Azides; D008024:Ligands; D009944:Organoplatinum Compounds; D011725:Pyridines