[(Pb6I8){Mn(CO)5}6]2–: An Octahedral (M6X8)-like Cluster with Inverted Bonding

• DOI: 10.1021/acs.inorgchem.5b00170
• Publication Date: 2015-04-01T20:35:39Z
• Authors: Silke Wolf; Kevin Reiter; Florian Weigend; Wim Klopper; Claus Feldmann
• Keywords: Electronegativity; Mulliken population analysis

[BMIm]2[{PbMn(CO)5)}6I8] (BMIm: 1-butyl-3-methylimidazolium) is obtained by ionic liquid mediated reaction of PbI2 and Mn2(CO)10. Central a cubelike (Pb6I8) unit containing nonfilled Pb6 octahedron. Each Pb this terminated on its outside Mn(CO)5, exhibiting Pb-Mn metal-to-metal bonding (280 pm). Structurally, the similar to well-known octahedral (M6Xn) cluster-type family (M = Zr, Nb, Ta, Mo, W; X Cl, Br, I). In contrast most cluster compounds, such as W6Br12 ([W6Br8]Br2/1Br4/2, according Niggli notation) or carbonyl [Sn6{Cr(CO5)6}](2-), however, central octahedron in [{PbMn(CO)5)}6I8](2-) does not exhibit any bonding. Structure title compound are validated single-crystal structure analysis, energy-dispersive X-ray analysis (EDX), infrared spectroscopy (FT-IR), density functional theory (DFT) calculations. Based isolobal principle, electronegativity considerations, bond lengths, DFT calculations including Mulliken population natural (NPA), sum, charge distribution best reflected an oxidation state +1.