Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Advanced Materials Laboratory, Fudan University, Shanghai 200433, China.
Phys Chem Chem Phys. 2009 Oct 21;11(39):8714-20. doi: 10.1039/b909999a. Epub 2009 Jul 31.
Matrix isolation infrared spectra and quantum chemical calculations of the copper dioxygen/ozonide complexes, CuO(5), CuO(4) and CuO(4)(-) are reported. These oxygen-rich species were prepared by reactions of laser-evaporated copper atoms with dioxygen or ozone in solid argon. The CuO(5) complex was determined to be a superoxo copper ozonide complex, in which both the superoxo and ozonide ligands are side-on bonded to the copper center. It was predicted to have a (4)A(1) ground state with planar C(2v) symmetry. Besides CuO(5), the previously observed CuO(4) complex and a new CuO(4)(-) anion were also formed. The CuO(4) complex was characterized to be a side-on bonded copper disuperoxide complex, which has a (4)B(2u) ground state with planar D(2h) symmetry. The CuO(4)(-) anion was characterized to be a disuperoxide complex with both superoxide ligands coordinated to the Cu center in an end-on fashion having a (3)A(u) ground state with planar C(2h) symmetry.
报道了铜双氧/臭氧化物配合物 CuO(5)、CuO(4)和 CuO(4)(-)的矩阵隔离红外光谱和量子化学计算。这些富氧物种是通过激光蒸发铜原子与固体氩气中的氧气或臭氧反应制备的。确定 CuO(5)配合物为超氧铜臭氧化物配合物，其中超氧和臭氧配体均以侧接方式与铜中心键合。它被预测具有平面 C(2v)对称的 (4)A(1)基态。除了 CuO(5)之外，还形成了先前观察到的 CuO(4)配合物和新的 CuO(4)(-)阴离子。CuO(4)配合物被表征为侧接键合的铜双过氧化物配合物，具有平面 D(2h)对称的 (4)B(2u)基态。CuO(4)(-)阴离子被表征为具有端接方式配位的双过氧化物配合物，其中两个超氧配体与 Cu 中心配位，具有平面 C(2h)对称的 (3)A(u)基态。
