Triosmium clusters containing ligands derived from tropone (cycloheptatrienone): molecular structure of an oxidative addition product [Os3H(µ3-C7H5O)(CO)9]

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Abstract
Tropone (cycloheptatrienone, C7H6O) reacts in refluxing cyclohexane with [Os3H2(CO)10] to give the oxidative addition product [Os3H(C7H5O)(CO)10](1), also formed from [Os3(CO)10(MeCN)2], and the insertion product [Os3H(C7H7O)(CO)10](2). Structures based on spectroscopy are discussed. Compound (1) decarbonylates to [Os3H(C7H5O)(CO)9](3), the X-ray structure of which shows that the µ3-troponyl ligand is involved in a µ-η2-vinyl type bridge between two Os atoms and a donation through the oxygen atom of the ketonic group to the third Os atom. Hydrogenation of cluster (1) and decarbonylation of cluster (2) lead to the derivatives [Os3H2(C7H6O)(CO)9](4) and [Os3(C7H8O)(CO)9](5). Cluster (4) is directly related to the reported structures [Os3H2(C6H4O)(CO)9] from phenol and [Os3H2(C6H8O)(CO)9] from cyclohexanone. All five products from tropone contain Os–O bonds and the chemistry is quite unlike any known tropone–transition metal chemistry.

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