Cationic, Neutral, and Anionic Platinum(II) Complexes Based on an Electron-Rich PNN Ligand. New Modes of Reactivity Based on Pincer Hemilability and Dearomatization
作者:Dana Vuzman、Elena Poverenov、Linda J. W. Shimon、Yael Diskin-Posner、David Milstein
DOI:10.1021/om8001069
日期:2008.6.9
reactivity of new Pt(II) complexes, including anionic d8 complexes, based on the electron-rich, hemilabile PNN-type pincer ligand C5H3N-2-(CH2PtBu2)(CH2NEt2) are described. Formation of these complexes involves dearomatization/aromatization processes of the ligand. The chloride complex [(PNN)PtCl]+Cl− (1) was prepared and reacted with the base tBuOK to give the deprotonated, neutral chloride complex
基于富电子,半不稳定的PNN型钳形配体C 5 H 3 N-2-(CH 2 P t Bu 2)(CH 2)的新Pt(II)配合物(包括阴离子d 8配合物)的合成和反应性描述了NEt 2)。这些复合物的形成涉及配体的脱芳香化/芳香化过程。氯化物配合物[(PNN)氯铂酸] +氯- (1)溶液并与所述碱反应吨丁醇钾,得到去质子化,中性氯化物络合物(PNN *)氯铂酸(2)(PNN * = C 5 H ^ 3 N- 2-(CHPt Bu 2)(CH 2 NEt 2))。的反应2与Ñ丁基锂,得到相应的中性氢化物络合物(PNN *)PTH(3),将其容易地由三氟甲磺酸质子化,得到阳离子氢化物配合物[(PNN)PTH] +光学传递函数- (4)。出乎意料的是,配合物2与1当量的RLi的反应导致螯合环的打开,从而得到相应的阴离子,脱芳构化的配合物Li + [(PNN *)Pt(Cl)(R)] -(R =甲基,5