Huang Wei, Xu Wen-Hua, Schwarz W H E, Li Jun
Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Tsinghua University , Beijing 100084, China.
Inorg Chem. 2016 May 2;55(9):4616-25. doi: 10.1021/acs.inorgchem.6b00442. Epub 2016 Apr 13.
Metal tetraoxygen molecules (MO4, M = Fe, Ru, Os, Hs, Sm, Pu) of all metal atoms M with eight valence electrons are theoretically studied using density functional and correlated wave function approaches. The heavier d-block elements Ru, Os, Hs are confirmed to form stable tetraoxides of Td symmetry in (1)A1 electronic states with empty metal d(0) valence shell and closed-shell O(2-) ligands, while the 3d-, 4f-, and 5f-elements Fe, Sm, and Pu prefer partial occupation of their valence shells and peroxide or superoxide ligands at lower symmetry structures with various spin couplings. The different geometric and electronic structures and chemical bonding types of the six iso-stoichiometric species are explained in terms of atomic orbital energies and orbital radii. The variations found here contribute to our general understanding of the periodic trends of oxidation states across the periodic table.
利用密度泛函和相关波函数方法对所有具有八个价电子的金属原子M（M = Fe、Ru、Os、Hs、Sm、Pu）的金属四氧分子（MO4）进行了理论研究。较重的d区元素Ru、Os、Hs被证实能在具有空金属d(0)价层和闭壳层O(2-)配体的(1)A1电子态中形成Td对称的稳定四氧化物，而3d、4f和5f元素Fe、Sm和Pu在具有各种自旋耦合的较低对称结构中更倾向于其价层的部分占据以及过氧化物或超氧化物配体。从原子轨道能量和轨道半径的角度解释了这六种等化学计量物种不同的几何和电子结构以及化学键类型。这里发现的变化有助于我们对整个周期表中氧化态的周期性趋势有更全面的理解。
