双核及单核铂（IV）叠氮基三唑配位化合物的溶剂依赖性反应活性与光化学
Solvent-Dependent Reactivity and Photochemistry of Dinuclear and Mononuclear Platinum(IV) Azido Triazaolato Complexes.
作者信息
Yao Kezi, Bertran Arnau, Morgan Jacques, Greenhalgh Charlotte, Edkins Katharina, Bowen Alice M, Farrer Nicola J
机构信息
Chemistry Research Laboratory University of Oxford 12 Mansfield Road Oxford OX1 3TA United Kingdom.
Centre for Advanced Electron Spin Resonance and Inorganic Chemistry Laboratory, Department of Chemistry University of Oxford South Parks Road Oxford OX1 3QR United Kingdom.
出版信息
Eur J Inorg Chem. 2021 Apr 15;2021(14):1397-1404. doi: 10.1002/ejic.202100041. Epub 2021 Mar 16.
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.
铂（IV）叠氮配合物 -[Pt(py)(N)(OH)]（）与1,4 - 二苯基 - 2 - 丁炔 - 1,4 - 二酮在乙腈中的反应生成了中间过氧化物桥联的二聚铂（IV）叠氮三唑物种（），该物种已通过X射线晶体学进行了表征。然而，如果 和 的反应在甲醇中进行，则会导致分解。在乙腈中随着时间的推移，二聚体（）会转化为单核配合物 -[Pt(py)(N)(三唑)(OH)]（/），它们处于动态交换中。如果重新悬浮在质子溶剂（甲醇、水）中，/会缓慢（22天）不可逆地重排为含有形式上N,O - 螯合配体的环化铂（IV）物种 。在 - 甲醇中，/向 的转化可以通过可见光照射加速（384倍），尽管持续照射也会产生N 和OH自由基，并且[-N]物种可以通过电喷雾电离质谱（ESI - MS）轻松检测到。溶剂的选择对 和 之间的环加成反应以及所得配合物的稳定性都有显著影响。
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