- Solid state molecular structures of transition metal hexafluorides
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Single-crystal structure determinations of all nine transition metal hexafluorides (Mo, Tc, Ru, Rh, W, Re, Os, Ir, and Pt) at -140°C are presented. All compounds crystallize alike and have the same molecular structure. The bond length sequence rW-F ? rRe-F ? rOs-F Ir-F Pt-F is confirmed and paralleled by the sequence rMo-F ? rTc-F ? rRu-F Rh-F. Within the limits of precision, no systematic deviation from octahedral symmetry can be established. DFT and ab initio calculations predict octahedral structures for MoF6 and RhF6 and tetragonally distorted structures for ReF6 and RuF6. The energy barrier toward octahedral structures is only 2.5 kJ mol-1 in the two latter cases. Calculated electron affinities are in the sequence MoF6 6 6 6 with a value of 6.98 eV for the latter. O2 +RhF6- crystallized in an undisordered manner in P1, isostructural to the low-temperature form of O2 +AuF6-. RhF6- has a D4h, compressed octahedral structure, while AuF6 - is essentially octahedral. The absorption spectrum of TcF 6 and the 19F and 195NMR spectra of PtF 6 are presented.
- Drews, Thomas,Supel, Joanna,Hagenbach, Adelheid,Seppelt, Konrad
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- Spectroscopic Studies on the Hexafluorides of Rhenium, Osmium, Iridium, and Platinum isolated in Low-temperature Matrices
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The compounds ReF6, OsF6, IrF6, and PtF6 have been isolated as monomeric species in inert-gas matrices at low temperatures, and characterised by i.r. spectroscopy.Subsequent u.v.-visible studies reveal a complex pattern of electronic absorptions, and a detailed assignment of these in terms of charge transfer, d-d, and intra-configurational transitions is presented.
- Holloway, John H.,Stanger, Gillian,Hope, Eric G.,Levason, William,Ogden, J. Steven
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p. 1341 - 1346
(2007/10/02)
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