Preparation of Pyranylidene Complexes of Ruthenium

The reaction of the chloro-complex RuCl(eta(5)-C5H5)(PPh3)[P(OMe)(3)] with alkylpropiolates HC equivalent to CCOOR1 in alcohol R2OH affords pyranylidene derivatives [Ru(eta(5)-C5H5){=C(COOR1)C(H)C(H)C(OR1)O}(PPh3){ P(OMe)(3)}]BPh4 (1, 3) and alkoxycarbene complexes [Ru(eta(5)-C5H5){=C(OR2)(CH(2)COOR1)}(PPh3){P(OMe)(3)}]BPh4 (2, 4). A reaction path for the formation of compounds 1-4, involving reactions on a vinylidene intermediate complex, is also discussed. The complexes were characterized spectroscopically (IR and H-1, C-13, P-31 NMR) and by X-ray crystal structure determination of [Ru(eta(C5H5)-C-5){=C(COOMe)C(H)C(H)C(OMe)O}(PPh3){P(OMe)(3)}] BPh4 (1).