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The thermal reaction of Ru 3 (CO) 12 with dibenzylideneacetone PhCHdCHCOCHdCHPh (1) was studied. From the solution, the trinuclear complexes Ru 3 (CO 7) were isolated, and the precipitate was found to contain the tetranuclear complex Ru 4 (CO 8). The organic ligand in complexes realizes different coordination modes forming five-membered oxaruthenacycle, η 3 -coordinated dihydropyran cycle, η 4 -coordinated diene, or oxadiene fragments. Complex 7 is unstable and undergoes chemical transformations yielding complex 8. Reversible changes occur with complex 8 upon dissolution in acetone, and binuclear complex Ru 2 (CO) 4 (η-Od CMe 9) is formed. The central Ru 2 O 2 cycle in complex 8 is cleaved and the formed vacant coordination site is occupied by an acetone molecule in complex 9. Complexes 6-9 were characterized by IR and 1 H NMR spectroscopy, and their structures were determined by single-crystal X-ray diffraction analysis. The structural and spectroscopic features and possible pathways of the complexes' transformations are discussed.

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