Solvent-dependent reactivity and photochemistry of dinuclear and mononuclear platinum (IV) azido triazaolato complexes

Kezi Yao, Arnau Bertran, Jacques Morgan, Charlotte Greenhalgh, Katharina Edkins, Alice Bowen, Nicola J. Farrer

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Reaction between the platinum(IV) azido complex trans,trans,trans-[Pt(py)2(N3)2(OH)2] (1) and 1,4-diphenyl-2-butyne-1,4-dione 2 in MeCN produces the intermediate peroxide-bridged dimeric platinum(IV) azido triazolato species (5), which has been characterised by X-ray crystallography. However, if the reaction between 1 and 2 is conducted in MeOH it results in decomposition. Over time in MeCN, dimer (5) converts into mononuclear complexes trans,trans,trans-[Pt(py)2(N3)(triazole)(OH)2] (3 a/3 b), which are in dynamic exchange. If resuspended in protic solvents (MeOH,H2O), 3 a/3 b undergo a slow (22 d) irreversible rearrangement to a cyclised platinum(IV) species 4 which contains a formally N,O-chelated ligand. Conversion of 3 a/3 b to 4 in d4-MeOH can be accelerated (384x) by irradiation with visible light, although continued irradiation also produces N3. and OH. radicals, and the [4-N3]+ species can be readily detected by ESI-MS. Solvent choice significantly effects both the cycloaddition reaction between 1 and 2, and the stability of the resultant complexes.
Original languageEnglish
Pages (from-to)1397-1404
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Issue number14
Early online date1 Mar 2021
Publication statusPublished - 15 Apr 2021


  • Azides
  • Photoactivity
  • Platinum
  • Radicals
  • Structure elucidation


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