Binuclear Zinc Complexes with Radical-Anionic Diimine Ligands

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