Inorganic Chemistry, Vol.40, No.27, 7014-7019, 2001
Reactions of the protonated dinuclear ruthenium complex [{(eta(5)-C5H3)2(SiMe2)(2)}Ru-2(CO)(4)(mu-H)](+) with nucleophiles
Complex [{(eta (5)-C5H3)(2)(SiMe2)(2)}Ru-2(CO)(4)(mu -H)]+BF4-(1H(+)BF(4)(-)), which features a protonated Ru-Ru bond, reacts with F- to give (eta (5)-C5H5)(2)Ru-2(CO)(4) (2), resulting from the cleavage of both SiMe2 groups, with I- tu give the Ru-Ru cleaved product {(eta (5)-C5H3)(2)(SiMe2)(2)}Ru-2(CO)(4)(H)(I) (3), and with phosphines (PEt3, PMe2Ph) to give [{(eta (5)-C5H3)(2)(SiMe2)(2)}Ru-2(CO)(4)(H)(PR3)](+) (4a-b). Reaction of 1H(+)BF(4)(-) and NaOMe in THF generates {(eta (5)-C5H4)(2)SiMe2)Ru-2(CO)(4) (5), resulting from the cleavage of a single SiMe2 group, while the reaction of 1H(+)BF(4)(-) and NaOMe in MeOH generates {mu-eta (5):eta (5)-(C5H3SiMe2OMe)(C5H4)SiMe2}Ru-2(CO)(4) (6), resulting fron) the partial cleavage of a SiMe2 group. Reaction of 1H(+)BF(4)(-) and NaSR (R = Me, Et) in THF generates {(eta (5)-C5H3)(2)(SiMe2)(2)}Ru-2(CO)(4)(H)(SR) (R = Me, Et; 7a-b), which undergoes rearrangement upon contact with neutral and basic alumina or silica to give complexes {mu-eta (5):eta (1):eta (5)-(C5H3C=O)(C5H4)(SiMe2)(2)O}Ru-2(mu -SR)(CO)(3) (R = Me, Et; 8a-b). Molecular structures of 4a, 6, and 8a as determined by X-ray diffraction studies are also presented.