CHEMISTRY OF DODECACARBONYLTRIRUTHENIUM .I. ACETYLENE DERIVATIVES OF DODECACARBONYLTRIRUTHENIUM

Substitutions of carbonyl groups in Ru3(CO)12 by diphenylacetylene and tetraphenylcyclopentadienone are described. Nine compounds, six of which are trinuclear ruthenium carbonyl acetylenes, were isolated from the reaction with diphenylacetylene in inert solvents. In methyl alcohol two Ru3(CO)8(C2Ph2)2 isomers were obtained, a violet one having only terminal carbonyls and an orange-yellow one with bridging carbonyl groups. The thermal decomposition of the products and replacements of carbonyl groups with basic ligands (mainly triphenylphosphine) were studied. A compound Ru3(CO)5(C2Ph2)2(PPh3)3, containing bridging carbonyl groups, is also described. The greater tendency of the ruthenium carbonyl than of iron carbonyl to retain the trinuclear cluster in these reactions is discussed, with emphasis on the fact that the ruthenium carbonyl can give rise to bridged carbonyl compounds even when such groups are not present in the original structure. © 1969.