Binuclear Zinc Complexes with Radical-Anionic Diimine Ligands

The reactions of (dpp-BIAN)Zn−Zn(dpp-BIAN) (1) with PhCCH and of [(dpp-BIAN)Zn(μ-I)]2 (2) with potassium hydride yield the binuclear complexes [(dpp-BIAN)Zn(μ-CCPh)]2 (3) and [(dpp-BIAN)Zn(μ-H)]2 (4), respectively (dpp-BIAN = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene). Complex 3 is also obtained by thermal dehydrogenation of [dpp-BIAN(H)]Zn(CCPh) (5), which in turn can be prepared by reacting ZnI2 with equimolar amounts of [dpp-BIAN(H)]Na and PhCCNa. The paramagnetic compounds 3 and 4 have been characterized by ESR spectroscopy; the diamagnetic complex 5, by 1H NMR spectroscopy. The molecular structures of 3 and 4 have been determined by single-crystal X-ray diffraction. The electronic structure of complex 4 has been examined by DFT.

与PhC₆H₄CH反应的(dpp-BIAN)Zn−Zn(dpp-BIAN) (1)以及与氢化钾反应的[(dpp-BIAN)Zn(μ-I)]₂ (2)分别生成双核配合物[(dpp-BIAN)Zn(μ-C₆H₄Ph)]₂ (3)和[(dpp-BIAN)Zn(μ-H)]₂ (4)（其中dpp-BIAN代表1,2-双[(2,6-二异丙基苯基)亚胺]蒽醌）。复合物3还可以通过[dpp-BIAN(H)]Zn(C₆H₄Ph) (5)的热脱氢反应得到，该化合物可由ZnI₂与等摩尔量的[dpp-BIAN(H)]Na和PhC₆H₄CNa反应制备。具有顺磁性的化合物3和4已通过ESR光谱进行表征；抗磁性的复合物5则通过¹H NMR光谱进行鉴定。复合物3和4的分子结构通过单晶X射线衍射测定；复合物4的电子结构则通过DFT计算进行研究。