New Synthetic Routes to 2:η2:η2-C6H6)> (M = Ru or Os)

Article abstract of DOI:10.1039/DT9930000981

A new, more convenient route to the benzene cluster 2:η²:η²-C6H6)> directly from has been established.Triruthenium dodecacarbonyl, , undergoes reaction with Me3NO-CH2Cl2 in the presence of cyclohexa-1,3-diene to give the clusters and 2:η²:η²-C6H6)> in moderate yield.Triosmium dodecacarbonyl does not react similarly, but from the reaction of with cyclohexa-1,3-diene a key intermediate compound 4-C6H8)> has been isolated and the solid-state structure of its acetonitrile solvate established by single crystal X-ray dif fraction analysis at 150 K.The structure is monoclinic, space group P2₁/n, with a = 8.932(8), b = 17.387(13), c = 14.833(15) Angstroem, β = 105.69(6) deg and Z = 4.The three osmium atoms form a regular triangle with a mean Os-Os distance of 2.877(12) Angstroem.Two osmium atoms, Os(1) and Os(2), are co-ordinated to four carbonyl ligands and one, Os(3), co-ordinates to two carbonyl ligands.All carbonyl ligands are terminal and approximately linear.The cyclohexadiene ligand is η⁴ co-ordinated to Os(3) via the 1,3-diene moiety, donating four electrons in total.On thermolysis, this compound is converted to and then eventually to 2:η²:η²-C6H6)> by established means.

Full text of DOI:10.1039/DT9930000981

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