单核铜(II)过氧化物配合物的电子和几何结构的相关性。
Correlation of the electronic and geometric structures in mononuclear copper(II) superoxide complexes.
机构信息
Department of Chemistry, Stanford University , Stanford, California 94305, United States.
出版信息
Inorg Chem. 2013 Nov 18;52(22):12872-4. doi: 10.1021/ic402357u. Epub 2013 Oct 28.
Abstract
The geometry of mononuclear copper(II) superoxide complexes has been shown to determine their ground state where side-on bonding leads to a singlet ground state and end-on complexes have triplet ground states. In an apparent contrast to this trend, the recently synthesized (HIPT3tren)Cu(II)O2(•-) (1) was proposed to have an end-on geometry and a singlet ground state. However, reexamination of 1 with resonance Raman, magnetic circular dichroism, and (2)H NMR spectroscopies indicate that 1 is, in fact, an end-on superoxide species with a triplet ground state that results from the single Cu(II)O2(•-) bonding interaction being weaker than the spin-pairing energy.
摘要
单核铜（II）过氧化物配合物的几何形状已被证明决定其基态，其中侧键合导致单重态基态，而端式配合物具有三重态基态。与这一趋势明显相反，最近合成的（HIPT3tren）Cu（II）O2（•-）（1）被认为具有端式几何形状和单重态基态。然而，用共振拉曼、磁圆二色性和（2）H NMR 光谱学重新研究 1 表明，1 实际上是一种端式超氧化物物种，具有三重态基态，这是由于单个 Cu（II）O2（•-）键合相互作用比自旋配对能弱。
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