The chemistry of polynuclear compounds. Part 29. Products of the reaction of triruthenium and triosmium dodecacarbonyls with water

Abstract

The reaction of triruthenium dodecacarbonyi. [ Ru,(CO),,], with water leads to the formation of the tetranuclear hydrides cc-[Ru4(CO),,H4] and a-[Ru,(CO)~,H~]. The significance of this reaction to the possible activation of alkanes is discussed. The corresponding reaction of [Os,(CO>,,] leads to the isolation of clusters based on three, four, five, six, and seven metal atoms, viz. [Os,(CO),,H(OH)]. [OS~(CO)~,H,]. [OS,(CO),~H~], [ O S ~( C O ) ~~H ~' J , [OS~(CO)~~H,], [OS~(CO)~~H,], and [OS,C(CO)~,H,].The probable structures of these polynuclear osmium carbonyls are discussed and compared with those of the previously characterized osmium cluster carbonyls.

New pentanuclear complex Ru5(CO)11(µ4-O)(µ 3-H)(p-MeC6H4C(O)C(H)=CPh)3·transformations of the triruthenium cluster Ru3(CO)12 in thermal reactions with α,β-unsaturated carbonyl compounds

“…Thermal reactions of Ru 3 (CO) 12 with functionalized olefins, in particular, with oxadienes, which we have stud ied earlier, 4-10 occur nonselectively to form a large num ber of products. Under drastic reaction conditions, the Ru 3 (CO) 12 cluster is decomposed to give complexes with different nuclearities (from mononuclear to hexanuclear).…”

“…Thermal reactions of Ru 3 (CO) 12 with unsaturated or ganic compounds afford a great variety of complexes. On the one hand, ligands undergo various transformations, viz., dehydrogenation, dimerization, isomerization, etc.…”

“…Under drastic reaction conditions, the Ru 3 (CO) 12 cluster is decomposed to give complexes with different nuclearities (from mononuclear to hexanuclear). The formation of five membered oxaruthenacycles and dihydropyran rings from two molecules of the starting oxadiene is typical of this organic ligand.…”

“…Complex 1 was prepared by the reaction of Ru 3 (CO) 12 with 3 phe nyl 1 p tolylprop 2 en 1 one. We consider the structure of complex 1 in the light of structural analogies with other polynuclear complexes, which we have prepared earlier 4-6 by the reactions of Ru 3 (CO) 12 with the oxadiene ligands. These data contribute to the overall picture of thermal transformations of the cluster.…”

Di-μ-hydrido-hexadecacarbonylpentaosmium

“…NMR measurements by Eady, Johnson & Lewis (1977) indicate that there are two equivalent edge-bridging hydrides; from the disposition of the carbonyl ligands they probably bridge the two long Os-Os bonds [Os(1)-Os(4) and Os(2)-Os (4)]. If the two Os-H-Os bridges are considered to be two-electron three-centre bonds, a structure based on a square pyramid of Os atoms obeys the 18-electron rule overall, and would probably have been predicted on the basis of Wade's theory.…”