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

Yao, Kezi and Bertran, Arnau and Morgan, Jacques and Greenhalgh, Charlotte and Edkins, Katharina and Bowen, Alice and Farrer, Nicola J. (2021) Solvent-dependent reactivity and photochemistry of dinuclear and mononuclear platinum (IV) azido triazaolato complexes. European Journal of Inorganic Chemistry, 2021 (14). pp. 1397-1404. ISSN 1434-1948 (https://doi.org/10.1002/ejic.202100041)

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Abstract

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.

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