C–C coupling of CH activated polar vinyl monomers by a pentaruthenium cluster complex

Publication date: Available online 16 September 2019Source: Journal of Organometallic ChemistryAuthor(s): Richard D. Adams, Claire M. Prince, Mark D. Smith, Jonathan D. Tedder, Nutan D. WakdikarAbstractReactions of Ru5(CO)15(μ5-C), 1 with the polar vinyl monomers (PVM), methyl acrylate, vinyl acetate and N,N-dimethylacrylamide proceed by cluster opening additions accompanied by CH activation in the vinyl group of the PVM to yield olefin-activated complexes such as Ru5(μ5-C)(CO)14[η2-OCO(Me)CHCH](μ-H), 2, Ru5(μ5-C)(CO)14[η2-(MeCO2)CCH2](μ-H), 3 and Ru5(μ5-C)(CO)14[η2-OC(NMe2)CHCH](μ-H), 6. In this work we have investigated the nature of the addition and coupling/cross-coupling of a second PVM to the CH activated PVM in the complexes 2, 3, and 6. The products consist of C–C coupled diolefin complexes that have been transformed into η3-allyl ligands by shifts of the hydrogen atoms in the C–C coupled ligands. Nine new complexes of Ru5(μ5-C)(CO)13[η3-1-anti, 3-anti-(MeO)CO–C3H3-η1-OC(OMe)CH2](μ-H), 8; Ru5(μ5-C)(CO)13[η3-1-anti, 3-syn-(MeO2C)CH2C3H3–CH2-η1-OC(OMe)](μ-H), 9; Ru5(μ5-C)(CO)12[μ-η3-OC(OMe)CHCH][η2-CHCHCO2Me](μ-H), 10; Ru5(μ5-C)(CO)13[η3-1-syn, 3-anti-(MeO2C)C3H3-η1-OC(OMe)CH2](μ-H), 11; Ru5(μ5-C)(CO)13[η3-1-syn, 3-anti-Me2NCO–C3H3-η1-O=CNMe2CH2](μ-H), 12; Ru5(μ5-C)(CO)13[η3-1-anti, 3-syn-(Me2N)C(=O)–C3H3–CH2-η1-OC(NMe2)](μ-H), 13; Ru5(μ5-C)(CO)12[μ-η3-OC(NMe2)CHCH][η2-CHCHCO2Me](μ-H), 14; Ru5(μ5-C)(CO)13[η3-1-ant...

Source: Journal of Organometallic Chemistry - September 18, 2019 Category: Chemistry Source Type: research