At the use of photochemical and thermochemical activation new p-complexes of chromium, molybdenum, and tungsten were prepared containing in the coordination sphere h 2 -and h 4 -molecules of 4-methyl-3-penten-2-one. Nonempirical methods were applied to calculation of the energy parameters of the coordinated molecules, and the factors governing the h 2 -and h 4 -coordination of the oxodiene system were established. A thermochemical study was performed on the 4-methyl-3-penten-2-one h 4 -coordination product with carbonyl metal core. A scheme of the thermal decomposition was suggested for the iron (0) h 4 -(4-methyl-3-penten-2-one)tricarbonyl.A development of new preparative procedures based on the chemo-, regio-, and stereoselective addition reactions is among the most prominent trends in the modern synthetic chemistry. The interest attracted by this field of the synthetic organic and organometallic chemistry originates from the maximum atomic efficiency and atom-saving [1] of the addition reactions, especially of those occurring strictly at the definite structural fragments of substrates.We showed formerly that conjugated oxo-and azadienes located in the coordination sphere of the transition metals were involved in dialkyl phosphines addition at the carbon-heteroatom double bond irrespective of the type of heterodiene coordination with the metal center [26].The equal reactivity of the coordinated heterodienes independent of hapticity of their bonding cannot be rationalized regarding the metal only as a protective group [36] since as we have established the bonding with the metal center results in significant changes in the geometry and electronic structure of the oxodiene ligand [7]. Obviously for successful intracomplex functionalizing of unsaturated molecules a detailed study is required on the factors governing the readiness of organometallic compounds formation and also on the thermal stability and reactivity of the unsaturated molecules within the coordination sphere of the transition metal.In the present study we approached these problems by investigation of reactions between the 4-methyl-3-penten-2-one (mesityl oxide) and iron(0) pentacarbonyl and hexacarbonyls of metals of VIB group under both photochemical and thermochemical activation.Under UV irradiation of a THF solution containing a homocarbonyl complex of a transition metal and mesityl oxide products were obtained of h 2 -coordination of aenone IaId. The p-type coordination of the olefin ligand with the metal atom was confirmed by the appearance in the IR spectra of the reaction products of the absorption bands of the C=C bond coordinated to a metal center: 1560 (Ia), 1565 cm 1 (Id); in a free mesityl oxide the corresponding band was observed at 1640 cm 1 . In the region of the stretching vibrations of the C=O bond of the carbonyl ligands coordinated to the metal in the spectrum of compound Ia were observed four, and in the spectra of compounds Ib-Id five well resolved bands revealing that only one molecule of carbon monoxide was replaced in...