Chemistry of polynuclear compounds. Part XVIII. Some reactions of dodecacarbonyltriosmium and some related derivatives

Abstract

On prolonged heating in benzene under reflux dihalogenododecacarbonyltriosmium, Os₃(CO)₁₂X₂(X = Cl, Br, or I), yields the dihalogenodecacarbonyltriosmium derivative Os₃(CO)₁₀X₂. This is related to and is considered to be isostructural with Os₃(CO)₁₀(OMe)₂. Sodium borohydride reacts with Os₃(CO)₁₂Cl₂ to give the cyclic hydrido-derivative HOs₃(CO)₁₀Cl which is considered to be a member of the series of compounds typified by HOs₃(CO)₁₀(OMe). Certain tertiary phosphines L (L = PEt₃, PEt₂Ph, or PMePh₂) react with dodecacarbonyltriosmium to give mono-, di- and tri-substituted derivatives, Os₃(CO)₁₁L, Os₃(CO)₁₀L₂ and Os₃(CO)₉L₃. Halogenation and substitution of some of these derivatives are also described.