title: Metal-metal bonding and aromaticity in [M2(NHCHNH)3]2 (μ-E)2 (E = O, S; M = Nb, Mo, Tc, Ru, Rh).
abstract: The nature of M-M bonding and aromaticity of [M2(NHCHNH)3]2(μ-E)2 (E = O, S; M = Nb, Mo, Tc, Ru, Rh) was investigated using atoms in molecules (AIM) theory, electron localization function (ELF), natural bond orbital (NBO) and molecular orbital analysis. These analyses led to the following main conclusions: in [M2(NHCHNH)3]2(μ-E)2 (E = O, S; M = Nb, Mo, Tc, Ru, Rh), the Nb-Nb, Ru-Ru, and Rh-Rh bonds belong to "metallic" bonds, whereas Mo-Mo and Tc-Tc drifted toward the "dative" side; all these bonds are partially covalent in character. The Nb-Nb, Mo-Mo, and Tc-Tc bonds are stronger than Ru-Ru and Rh-Rh bonds. The M-M bonds in [M2(NHCHNH)3]2(μ-S)2 are stronger than those in [M2(NHCHNH)3]2(μ-O)2 for M = Nb, Mo, Tc, and Ru. The NICS(1)ZZ values show that all of the studied molecules, except [Ru2(NHCHNH)3]2(μ-O)2, are aromaticity molecules. O-bridged compounds have more aromaticity than S-bridged compounds. Graphical Abstract Left Molecular graph, and right electron localization function (ELF) isosurface of [M2(NHCHNH)3]2(μ-E)2(E = O, S; M = Nb, Mo, Tc, Ru, Rh).
authors.affiliation: College of Chemistry and Material Science, Hebei Normal University, Road East of 2nd Ring South, Shijiazhuang, 050024, China.|Key Laboratory of Inorganic Nano-Materials of Hebei Province, Shijiazhuang, 050024, China.
authors.forename: Xiuli
authors.initials: X
authors.lastname: Yan
authors.affiliation: College of Chemistry and Material Science, Hebei Normal University, Road East of 2nd Ring South, Shijiazhuang, 050024, China.|Key Laboratory of Inorganic Nano-Materials of Hebei Province, Shijiazhuang, 050024, China.
authors.forename: Lingpeng
authors.initials: L
authors.lastname: Meng
authors.affiliation: College of Chemistry and Material Science, Hebei Normal University, Road East of 2nd Ring South, Shijiazhuang, 050024, China.|Key Laboratory of Inorganic Nano-Materials of Hebei Province, Shijiazhuang, 050024, China.
authors.forename: Zheng
authors.initials: Z
authors.lastname: Sun
authors.affiliation: College of Chemistry and Material Science, Hebei Normal University, Road East of 2nd Ring South, Shijiazhuang, 050024, China. lixiaoyan326@163.com.|Key Laboratory of Inorganic Nano-Materials of Hebei Province, Shijiazhuang, 050024, China. lixiaoyan326@163.com.
authors.forename: Xiaoyan
authors.initials: X
authors.lastname: Li
keywords: Aromaticity; Metal–metal bond; Topological analysis of electron density
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