Unsaturated ether chelate complexes of ruthenium(II)

The complexes [Ru{eta(5)-C(5)Me(4)CH(2)O(CH2)(n)CH=CR(1)R(2)}(CO)(2)Cl] (2a R(1) = R(2) = H, n = 1; 2b R(1) = R(2) = H-i n = 2; 2c R(1) = H, R(2) = Me, n = 1; 2d R(1) = Me, R(2) = H, n = 1) were prepared by heating [Ru(eta(5)-C(5)Me(4)CH(2)Cl)(CO)(2)Cl] 1 with the appropriate unsaturated alcohol. Reaction of complexes 2 with AgBF4 led to loss of the chloride ligand acid the formation of the cationic chelate complexes [Ru{eta(5):eta(2)-C(5)Me(4)CH(2)O(CH2)(n)CH=CR(1)R(2)}(CO)(2)]BF4, with the double bond co-ordinated to the metal centre. Single-crystal X-ray structures determined for the complexes [Ru{eta(5):eta(2)-C(5)Me(4)CH(2)OCH(2)CH=CH2}(CO)(2)]BPh(4) and [Ru{eta(5):eta(2)-C(5)Me(4)CH(2)O(CH2)(2)CH=CH2}(CO)(2)]BF4 confirmed that the double bond was co-ordinated to the metal. The neutral chelate complex [Ru{eta(5):eta(2)-C(5)Me(4)CH(2)OCH(2)CH=CH2}(CO)Cl] was formed-on addition of trimethylamine N-oxide to a solution of 2a by the replacement of one of the carbonyl ligands with the alkene on the pendant arm.