Metal carbonyl-trifluorophosphine systems : X. Mono-and triruthenium carbonyls

Triruthenium dodecacarbonyl reacts with high pressure PF₃ or with PF₃/CO mixtures to yield two series of compounds. At high PF₃ pressures, the mononuclear species Ru(PF₃)_x(CO)_5−x (x = 5, 4 and 3) are the main products with only traces of Ru(PF₃)₂(CO)₃ and Ru(PF₃)(CO)₄ being found. With high carbon monoxide pressure and less PF₃, the species Ru₃(PF₃)_y(CO)_12−y (y = 0–6) are the main products. It is seen that Ru₃(CO)₁₂ can have up to six CO groups replaced sequentially before the cluster is broken followed by the formation of the mononuclear species. The evidence shows that the Ru(PF₃)_x(CO)_5−x species are stereochemically non-rigid.