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Solvent-Dependent Reactivity and Photochemistry of Dinuclear and Mononuclear Platinum(IV) Azido Triazaolato Complexes. | LitMetric
Reaction between the platinum(IV) azido complex ,-[Pt(py)(N)(OH)] () and 1,4-diphenyl-2-butyne-1,4-dione in MeCN produces the intermediate peroxide-bridged dimeric platinum(IV) azido triazolato species (), which has been characterised by X-ray crystallography. However, if the reaction between and is conducted in MeOH it results in decomposition. Over time in MeCN, dimer () converts into mononuclear complexes ,-[Pt(py)(N)(triazole)(OH)] (/), which are in dynamic exchange. If resuspended in protic solvents (MeOH,HO), / undergo a slow (22 d) irreversible rearrangement to a cyclised platinum(IV) species which contains a formally N,O-chelated ligand. Conversion of / to in -MeOH can be accelerated (384x) by irradiation with visible light, although continued irradiation also produces N and OH radicals, and the [-N] species can be readily detected by ESI-MS. Solvent choice significantly effects both the cycloaddition reaction between and , and the stability of the resultant complexes.
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