Isolation and Characterization of New Mono- and Polynuclear Complexes Formed in the Thermal Reaction of Ru3(CO)12 with 1-(4-Tolyl)-3- phenylaminoprop-2-en-1-one

摘要

Thermal reaction of Ru3(CO)12 with 1-(4-tolyl)-3-phenylaminoprop-2-en-1-one (1) proceeds in heptane with the formation of a number of new chelate mononuclear complexes, cis-Ru(CO)2[OdC- (Tol)CHdCHNPh]2 (2), cis-Ru(CO)2[OdC(Tol)CHdCNHPh][OdC(Tol)CHdCH-NPh] (3), and cis-Ru(CO)2[OdC(Tol)CHdCNHPh][OdC(Tol)CHdCHNPh] (4), isolated as the main products, along with minor amounts of the polynuclear clusters Ru5(CO)14(μ2-H)2(μ4-η1:η1:η2:η2- CCHC(Tol)dO) (5), Ru4(CO)11(μ2-H)2(μ4-η2:η2:η1:η2-NPhCCHC(Tol)dO) (6), and Ru4(CO)12- (μ4-η1:η1:η1:η1-NPhCHCC(Tol)dO) (7). Complexes of both series were characterized by a combination of spectroscopic IR and multinuclear NMR data and by single-crystal X-ray diffraction study, which revealed the existence of different types of metal-to-ligand bonding in these species. Chelated six-membered azaoxaruthenacycles are formed in 2-4 via N-H activation, while unexpected fivemembered oxaruthenacycles are formed in 3-6 due to Cβ-H activation. Among the products of the reaction, the butterfly cluster 7, with open-chain coordination of the ligand formed as a result of N-Hand CR-Hbond activation, is also isolated. Complex 5 proved to be the only reaction product in which the deamination of amino vinyl ketone 1 is observed. Possible pathways for the formation of the complexes obtained are discussed.