Darstellung, Schwingungsspektren und Normalkoordinatenanalysen der Dioxoosmate(VI) trans-[OsO2(CN)2(ox)]2-, transs-[OsO2(CN)2(mal)]2- und trans-[OsO2(CN)2(N2H2C2O2)]2- / Synthesis, Vibrational Spectra and Normal Coordinate Analysis of the Dioxoosmates(VI) frans-[OsO2(CN)2(ox)]2- , trans-[OsO2 (CN)2(mal)]2- and trans-[OsO2 (CN)2(N2H2C2O2)]2-
By careful acidification of the aqueous solution of trans-K2[OsO2(OH)4] in the presence of the required amount of cyanide ions with oxalic acid, malonic acid or oxamide the osmyl complexes trans-[OsO2(CN)2(ox)]2- (1), trans-[OsO2(CN)2(mal)]2- (2) und trans-[OsO2(CN)2(N2H2C2O2)]2- (3) are formed. The IR and Raman spectra of the (n-Bu4N) and (Et4N) salts of 1, 2 und 3 were measured at room temperature. Based on the molecular parameters of the X-ray determination of related complexes normal coordinate analyses have been performed and the vibrations were assigned. The valence force constants are fd(C≡N ) = 16.95, fd(Os=O) = 6.68 - 6.70, fd(Os-O) = 2.55 - 2.60, fd(Os-C) = 2.55 and fd(Os-N) = 2.30 mdyn/Å. For the chelate ligands, fd(C =0) ranges from 11.03 - 11.15, fd(C-O/N) from 4.86 - 5.05 and fd(C-C) from 4.07 - 4.70 mdyn/Å.