caa a22 4500 477085458 CHVBK 20180405111502.0 cr unu---uuuuu 170330e19960901xx s 000 0 eng 10.1007/BF01171195 doi (NATIONALLICENCE)springer-10.1007/BF01171195 Theoretical studies of (d-p)ρ bonding, electronic spectra, and reactivities in homo- and heterometallic clusters: [Mo3- n W n X4(H2O)9]4+ ( X [Elektronische Daten] O, S, Se, Te; n = 0-3) [Jun Li, Chun-Wan Liu, Jia-Xi Lu] Ab initio calculations with relativistic effective potentials have been carried out on 12 trinuclear molybdenum/tungsten cluster aqua ions [M3X4(H2O)9]4− (M3= Mo3, W3 for X = O, S, Se, Te; M3=Mo2W, MoW2 for X = O, S). The electronic structures and bonding pictures of l-12 are discussed in terms of the delocalized and localized molecular orbitals as well as the Mulliken populations, natural populations, and Mayer bond orders. It is shown that the (d-p)ρ bonding in the puckered six-membered ring of the [M3(µ-X)3] core arises from a closed continuous ring of three mutually adjacent localized (d-p-d)ρ bonds with strong interactions. It is these three-centered two-electron (d-p-d)ρ bonds that account for the unusual physicochemical properties and reactivities of these cluster compounds. The wavelengths and the assignment of electronic spectra have been given, and the relation between the wavelength shili and the (d-p)ρ bonding is discussed, The reactivities of the ligand substitution reactions and two kinds of addition reactions as weil as some kinetic and redox properties of these compounds are briefly discussed by taking advantage of this Iocalization (d-p-d)ρ a bonding picture. Plenum Publishing Corporation, 1996 Trinuclear cluster nationallicence Mo/W mixed compounds nationallicence reactivities nationallicence ab initio nationallicence (d-p-d)ρ bonding nationallicence chalcogen ligands nationallicence Li Jun The Stare Key Laboratory of Structural Chemistry of China and Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, Fujian, China aut Liu Chun-Wan The Stare Key Laboratory of Structural Chemistry of China and Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, Fujian, China aut Lu Jia-Xi The Stare Key Laboratory of Structural Chemistry of China and Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, Fujian, China aut Journal of Cluster Science Kluwer Academic Publishers-Plenum Publishers 7/3(1996-09-01), 469-500 1040-7278 7:3<469 1996 7 10876 https://doi.org/10.1007/BF01171195 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF01171195 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Li Jun The Stare Key Laboratory of Structural Chemistry of China and Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, Fujian, China aut NATIONALLICENCE 700 1- Liu Chun-Wan The Stare Key Laboratory of Structural Chemistry of China and Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, Fujian, China aut NATIONALLICENCE 700 1- Lu Jia-Xi The Stare Key Laboratory of Structural Chemistry of China and Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, Fujian, China aut NATIONALLICENCE 773 0- Journal of Cluster Science Kluwer Academic Publishers-Plenum Publishers 7/3(1996-09-01), 469-500 1040-7278 7:3<469 1996 7 10876 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer