Highly Polar Solvent-induced Disproportionation of a Cationic Pt(II)-Diimine Complex Containing an o-Semiquinonato
Highly Polar Solvent-induced Disproportionation of a Cationic Pt(II)-Diimine Complex Containing an o-Semiquinonato
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含有邻半醌的阳离子 Pt(II)-二亚胺配合物的高极性溶剂诱导歧化
DOI：
10.1039/c6dt00487c
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
張浩徹
中科院分区：
文献类型：
--
作者：
山田将太;松本剛;脇坂聖憲;張浩徹
化学单电子氧化[PtII(3,5- dtbcat)(DTBbpy)] (1) （3,5- dtbcat = 3,5-二叔丁基儿茶酚，DTBbpy = 4,4 ' -二叔丁基-2,2 ' -联吡啶）得到相应的顺磁配合物[PtII(3,5- dtbsq)(DTBbpy)]+PF6−(1(PF6))，这是配体中心氧化的结果。虽然配合物1在普通有机溶剂中相对稳定，但本研究表明，阳离子[1]+在DMSO和DMF等高极性溶剂中会发生前所未有的溶剂诱导歧化，导致1和游离苯醌的形成。
Chemical one-electron oxidation of [PtII(3,5-DTBCat)(DTBbpy)] (1) (3,5-DTBCat = 3,5-di-tert-butyl catecholato, DTBbpy = 4,4′-di-tert-butyl-2,2′-bipyridine) afforded the corresponding paramagnetic complex, [PtII(3,5-DTBSQ)(DTBbpy)]+PF6− (1(PF6)), as a result of ligand-centred oxidation. While complex 1 is relatively stable in common organic solvents, the present study demonstrates that cationic [1]+ is subject to an unprecedented solvent-induced disproportionation in highly polar solvents such as DMSO and DMF, which results in the formation of 1 and a free benzoquinone.