Chemistry of polynuclear compounds. Part XV. Halogenocarbonylruthenium compounds

Abstract

Oxidation of dodecacarbonyltriruthenium with halogens (X₂; X = Cl, Br, or I) gives the monomeric cis-Ru(CO)₄X₂, the dimeric Ru₂(CO)₆X₄, the trimeric Ru₃(CO)₁₂X₆ or the polymeric [Ru(CO)₂X₂]_n depending upon the reaction conditions. On the basis of i.r. studies, it would appear that the initial product in all of these oxidation is cis-Ru(CO)₄X₂ with subsequent polymerisation to give the dimeric and the trimeric compounds. No evidence for the formation of trans-Ru(CO)₄X₂ has been found. The dimeric, trimeric, and polymeric compounds are also produced from the reaction of the ruthenium trihalides (RuX₃) with carbon monoxide at atmospheric pressure and moderate temperatures. I.r. and mass spectral data are reported and various structural possibilities for these compounds are discussed.

Oxidation of (Ph₃P)₃Ru₃(CO)₉ with halogens give the mononuclear derivatives (Ph₃P)Ru(CO)₃X₂. These are unstable in solution and decompose with loss of carbon monoxide to give the dinuclear compounds [(Ph₃P)Ru(CO)₂X₂].