Darstellung, spektroskopische und elektrochemische Charakterisierung von Pentachloromonocarbonylosmat(IV), [OsCl5(CO)]- / Preparation, Spectroscopical and Electrochemical Characterization of Pentachlorom onocarbonylosm ate(IV), [OsCl5(CO)]-

Abstract

The first carbonyl compound of quadrivalent osmium [OsCl5(CO)]- is prepared by chlorination of trans-[OsX4(CO)2]- (X = Br, I) dissolved in CH2Cl2. It is reduced immediately by Br- and I- to give [OsCl5(CO)]2-. The standard potential [OsCl5(CO)]-/ [OsCl5(CO)]2- in acetonitrile referred to the saturated mercury-mercurous sulphate electrode is 0.623 V. The IR and Ra bands of [OsCl5(CO)]- are assigned according to point group C4v. Compared with the corresponding Os(III) complex there is a shift to higher frequencies of ν(CO) and ν(OsCI) of about 170 and 25 cm-1, whereas ν(OsC) and δ(OsCO) are lowered by 158 and 110cm-1, respectively. The electronic absorption spectrum shows six d - d bands coupled with vibrations in the near infrared region. The O - O transitions are calculated from the vibrational fine structure, taking into consideration shifts by 13C isotopic substitution. The lowest levels are confirmed by peaks in the electronic Raman spectrum. From the estimated Racah parameter B = 280 cm-1 the low nephelauxetic ratio β55 = 0.41 is deduced indicating the high covalency in [OsCl5(CO)]-. Owing to the strong oxidizing character of Os(IV) the intensive charge transfer transitions in the visible region are shifted bathochromicly by about 4000 cm1 in relation to corresponding bands of [OsCl5(CO)]2-.