| | 1 | Author
| W. Preetz, M. Bruns | Requires cookie* | | | Title
| Darstellung und spektroskopische Charakterisierung von Hexachloroosmat(V)  | | | | Abstract
| (TEA)[OSC16] is formed quantitatively by heating solid £RARAS-(TEA)[OsX4(CO)2] (X = Br, I) in a stream of chlorine at 120 °C, and can be purified by recrystallisation from CH2CI2 without decomposition. It is reduced immediately by acetone, methanol, CU, Br~, I -to give [OsCl6] 2 -. The standard potential [OsCl6] -/[OsCl6] 2 ~ in acetonitrile referred to the saturated mercury-mercurous sulphate electrode is 0.840 V. The IR and Ra bands of (TEA)[OsCl6], assigned according to point group Oh, are shifted to higher frequencies compared with (TEA)2[OsCle]. The excitation at 488.0 nm gives a resonance Raman spectrum exhibiting 6 overtones of vi and combination tones up to 4 J»I + v-0. The electronic absorption spectrum shows five spin-forbidden intraconfigurational transitions coupled with odd vibrational modes in the near infrared region. The spin-allowed 4 A2g -> 4 T2g, 4 Tig-transitions are observed at 347 and 305 nm. The excited levels can be fitted with the parameters A = 28500 cm-1 , B = 340 cm-1 , $ = 2500 cm 4 , allowing to calculate the nephel-auxetic ratio /J55 to 0.47. In the visible region extensive charge transfer transitions are observed. Based on the strong oxidizing character of Os(V) there is a bathochromic shift of corresponding bands of [OsClß]-in relation to [OsC^] 2-of about 6600 cm -1 and to the isoelectronic [ReCle] 2-of about 13700 cm -1 , respectively. From Jitiu->dt2g the optical electronegativity is calculated to a0pt(Os v) — 2.49. | | | |
Reference
| Z. Naturforsch. 38b, 680—686 (1983); eingegangen am 10. Februar 1983 | | | |
Published
| 1983 | | | |
Keywords
| Hexachloroosmate(V), Electronic Spectra, IR Spectra, Raman Spectra | | | |
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| default:Reihe_B/38/ZNB-1983-38b-0680.pdf | | | | Identifier
| ZNB-1983-38b-0680 | | | | Volume
| 38 | |
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