Mackay, Fiona S., Farrer, Nicola J., Salassa, Luca, Tai, Hui-Chung, Deeth, Robert J., Moggach, Stephen A., Wood, P. A. (Peter A.), Parsons, S. (Simon) and Sadler, P. J.. (2009) Synthesis, characterisation and photochemistry of PtIV pyridyl azido acetato complexes. Dalton Transactions, Vol.13 . pp. 2315-2325. ISSN 1477-9226

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Abstract

PtII azido complexes [Pt(bpy)(N3)2] (1), [Pt(phen)(N3)2] (2) and trans-[Pt(N3)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 (N3–Pt–N3 angle 146.7°) as a result of steric congestion at the Pt centre. The novel PtIV complexes trans, cis-[Pt(bpy)(OAc)2(N3)2] (4), trans, cis-[Pt(phen)(OAc)2(N3)2] (5), trans, trans, trans-[Pt(OAc)2(N3)2(py)2] (6), were obtained from 1–3via oxidation with H2O2 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 PtIV complexes exhibit greater absorption at longer wavelengths (ε = 9756 M−1 cm−1 at 315 nm for 4; ε = 796 M−1 cm−1 at 352 nm for 5; ε = 16900 M−1 cm−1 at 307 nm for 6, in aqueous solution) than previously reported PtIV 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 PtII and PtIV electronic and structural properties allowed further elucidation of the photochemistry of 4–6.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry R Medicine > RC Internal medicine > RC0254 Neoplasms. Tumors. Oncology (including Cancer)
Divisions:	Faculty of Science > Chemistry
Library of Congress Subject Headings (LCSH):	Platinum compounds -- Research, Cisplatin -- Research, Organoplatinum compounds -- Research, Ligands (Biochemistry) -- Research, X-ray crystallography, Magnetic resonance imaging, Ultraviolet spectroscopy, Density functionals
Journal or Publication Title:	Dalton Transactions
Publisher:	Royal Society of Chemistry
ISSN:	1477-9226
Date:	September 2009
Volume:	Vol.13
Page Range:	pp. 2315-2325
Identification Number:	10.1039/b820550g
Status:	Peer Reviewed
Access rights to Published version:	Restricted or Subscription Access
Funder:	Engineering and Physical Sciences Research Council (EPSRC), Scottish Enterprise (SE), Medical Research Council (Great Britain) (MRC), European Commission (EC)
Grant number:	G0701062 (MRC), EP/E000945X (EPSRC)
URI:	http://wrap.warwick.ac.uk/id/eprint/3368

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