Functionalised alkenylcarbene metal complexes (M = Ru, W, Cr) by activation of propargyl alcohol derivatives

The reaction of arene ruthenium(II) complexes [Ru(eta(6)-C6Me4R2)(PMe3)Cl-2 ] (1, R = Me; 1', R = H) with propargyl alcohol derivatives HC=C(H)(OH)(p-C 6H4-X) (a, X = HC=C(H)(OH); c, X = CHO; d, X = CH=CH2; e, X = CH=CH-CH=CH2) and methanol gives the (methoxy)-alkenylcarbene ruthenium complexes [Ru(et a(6)-C6Me4R2)(PMe3)(Cl) (=C(OMe)(CH=CH-p-C6H4-X)][PF6] (2a) and (2'c-e). Si milarly, the half-sandwich carbene complexes [Ru(eta(5)-C5H5(CO)(PPh3)(=C(O Me)(CH=CH-p-C6H4-X)][BF4] (4a and 4d) are obtained from [Ru(eta(5)-C3H5)(CO )(PPh3)(Cl)] (3) and propargyl alcohol derivatives a and d, respectively. T reatment of M(CO)(5)(THF) (M = W, Cr) with a and HC=C(H)(OH)-C4H2S-(OH)(H)C =CH (b) yields the monometallic complexes (CO)(5)M=C(OMe)(=C(OMe)(CH=CH-Ar- (OH)(H)C=CH)] (5a) (M = W; -Ar- = -C6H4-), 5b (M = W; -Ar- = -C4H2S-), and 7a (M = Cr; -Ar- = -C6H4-) as the major products, and the bimetallic comple xes (CO)(5)W=C(OMe)CH=CH-Ar-CH=CH(OMe)C=W(CO)(5) (6a) and (6b) as the minor products. Finally, the reaction of 5a and 5b with amines ((PrNH2)-Pr-i, Me 2NH, Et2NH), and diamines such as ethylene diamine and piperazine produces the expected amino alkenyl-tungsten complexes 9a-13a and 9b in high yields. (C) 2000 Elsevier Science S.A. All rights reserved.