Abstract--Ruthenium trichloride reacts with stoichiometric amounts of tertiary arsines in boiling ethanol to give paramagnetic complexes, RuCI3(Ph2RAs)~ (R = Me, Et, Pr, Bu), which react further with 2,2'-hipyridyl(bipy) and o-phenanthroline(phen) to yield brick red crystalline products, RuCI3 (N-N)(Ph2RAs) (N-N = bipy, phen). In the presence of excess arsine Ru(III) is reduced to Ru(II), and trichloro-bridged complexes of the formula [RuzCI3(Ph2RAs)6]CI are formed. These on treatment with carbonylated solutions of rhodium chloride produce yellow crystals of [Ru2Ch(Ph2RAs)6][RhCI2(CO)2] containing Ru(II) and Rh(l). Several dicarbonyl complexes cis-RuXz(CO)2(PhzRAs)2 (X = CI, Br; R = Pr. Bu) have also been isolated.

Osmium halide, (CI and Br) react with monotertiary arsines Ph2RAs (R=Me, Et, Pr and Bu) in alcoholic medium to give paxamagnetic octahedrat complexes of the type OsXaL a (X = CI, Br; L = PhzRAs) which further react with carbonmonoxide to give dihalo dicarbonyl complexes of osmium(II) of th 9 type OSX2(CO)2 Lz. Similarly, osmium halides react with tertiary arsines in tim presznc, of formald 9 to give monocarbonyl complexes of osmium(H) of the type OsX2 (CO)L a. SU'uctures have been assigned to all these compounds on the basis of IR and NMR studies. Keyw~ds. Osmium ; ~trboumoaoxido ; tcxtiary argines ; IR spectra ; NMR spectra.

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Die durch stöchiometrische Umsetzung von Ru‐trichlorid mit entsprechenden, tert. Arsinen gebildeten, paramagnetischen Komplexe (I) reagieren weiter mit Bipyridyl oder Phenanthrolin zu den kristallinen Derivaten (II).