C-O and C-S bond activation of allyl esters, ethers, and sulfides by low valent ruthenium complexes

Allyl carboxylates or ethers react with Ru(cod)(cot) (1) [cod: 1,5-cyclooct adiene, cot: 1,3,5-cyclooctatriene] in the presence of monodentate tertiary phosphines such as PMe3, PEt3, PMe3Ph or PMePh2 to give a series of neutra l (eta(3)-allyl)ruthenium(II) complexes Ru( eta(3)-C3H5)(OCOCF3)(PR3)(3) [P R3 = PEt3 (2a), PMe3 (2b), PMe2Ph (2c), PMePh2 (2d)], Ru(eta(3)-C3H5)(OCOR' )(PMe3)(3) [R' = Me (2e), Ph (2f)], Ru(eta(3)-syn-C3H4R)(OCOCF3)(PMe3)(3) [ R = Me (2g), Ph (2h)] and Ru(OAr)(eta(3)-C3H5)(PMe3)(3) [Ar = Ph (3a), C6H4 -o-Me (3b), C6H4-o-Et (3c), C6H4-o-OMe (3d)], whereas similar reactions of these allyl ethers, sulfides and carboxylates in the presence of the bident ate depe ligand [depe = 1,2-bis(diethylphosphino)ethane] afford the cationi c (eta(3)-allyl)ruthenium(II) complexes, [Ru(eta(3)-C3H5)(depe)(2)](+)[RY]( -) [RY = PhS (4a), MeS (4b), PhO (4c), CF,COO (4d), CH,COO (4e)]. Protonoly sis of all (eta(3)-allyl)ruthenium(II) and (eta(3)-crotyl)ruthenium(II) com plexes with HCL liberate propylene and trans-2-butene, respectively. Comple x 2a reacts with benzaldehyde to give 1-phenyl-3-butene-1-ol. Reaction of 2 b with CO forces the bonding mode of allyl moiety in 2a from eta(3) to eta( 1). (C) 1999 Elsevier Science B.V. All rights reserved.