Some reactions of dimethyl(1-naphthyl)phosphine with ruthenium and osmium compounds

Abstract

Hydrated ruthenium trichloride reacts with dimethyl(1-naphthyl)phosphine(L) to give mainly five-co-ordinate [RuCl₂L₃] and a small amount of [Ru₂Cl₃L₆]⁺, isolated as the salt with BPh₄^–, [RuCl₂L₃] readily takes up carbon monoxide to give [RuCl₂(CO)L₃] and also other ligands (Q) to give labile products [RuCl₂QL₃](Q = pyridine, 2-methylpyridine, 4-methylpyridine, acetonitrile, methyl isocyanide, or tetracyanoethylene). It shows no tendency to become internally metallated, however. Osmium tetroxide in the, presence of concentrated hydrochloric acid and alcohols reacts with L to give maroon mer-[OsCl₃L₃] in high yield, together with a small amount of the green internally metallated [OsCl₂(P–C)L₂], P–C = Me₂PC₁₀H₆^–. [OsBr₂(P–C)L₂] was also prepared. [OsCl₂(P–C)L₂] reacts with boiling 2-methoxyethanol in the presence of sodium hydroxide to give [Os(P–C)₂(CO)L] and with carbon monoxide in 2-methoxvethanol to give [OsCl₂(CO)L₂].