Organoruthenium( II ) complexes formed by insertion reactions of some vinyl compounds and conjugated dienes into a hydrido–ruthenium bond

The hydridoruthenium(II) complex [ RuCl(CO) H (PPh3)3](1) reacted easily with methyl acrylate and N,N-dimethylacrylamide to give the corresponding insertion products,[[graphic omitted]OMe}Cl(CO)(PPh3)2](2a) and [[graphic omitted]NMe2}Cl(CO)(PPh3)2](3), respectively. Similarly, complex (1) reacted with 2-vinylpyridine and 5-ethyl-2-vinylpyridine to afford the C1,N-chelating organoruthenium(II) complexes, [[graphic omitted]}Cl(CO)(PPh3)2](4a) and [[graphic omitted]}Cl(CO)(PPh3)2](5) respectively. Complexes (2a) and (4a) reacted with LiBr·H2O to give the analogous bromo-complexes. The conjugated dienes, penta-1,3-diene, isoprene, and methyl sorbate were treated with (1) to yield the η3-allylic ruthenium(II) complexes, [Ru{η3-R1C(H)C(R2)CHR3}Cl(CO)(PPh3)2][(6) R1= R3= Me, R2= H; (7) R1= R2= Me, R3= H; (8) R1= Et, R2= H, R3= CO2Me], respectively. On the basis of 1H and 13C-{lH} n.m.r. data, it has been concluded that the two PPh3 ligands in (2)–(5) are located trans to each other, whereas those in (6)–(8) are cis.