Reactions of 3-functional substituted propenes like allylbenzene, allyl alcohols and ethers, N-allylamines, N-allylamides and imides in the presence of ruthenium(III) complexes having 1,3-diketonate ligands, mainly 2,4-pentadionate, were examined. It was found that the course and rate of the reaction between substituted propene and ruthenium complex depend on donor—acceptor properties of the functional group combined with a C-3 propene carbon. When this group behaved like a medium or soft donor (allyl sulfides, N-allylimines), no double bond migration was observed, whereas Ru(acac) 3 underwent reduction to ruthenium(II) complexes of Ru(acac) 2L 2 type. Using a Δ-(+)-Ru(acac) 3 in reaction with propenes, the configuration of Ru(acac) 2L 2 complexes was determined and also a mechanism of their formation was proposed. The effect of donor—acceptor properties of solvents on reaction between a functional substituted propene and ruthenium complex was examined. Also, isotopic effects associated with a bond migration, the effect of substituents on isomerization rate of m- and p-substituted allyl aryl ethers in the presence of Ru(acac) 3 and the effect of ligands on catalytic activity of type Ru(1,3-diket) 3 complexes were studied.