Reactions of the Protonated Dinuclear Ruthenium Complex [{(η 5-C5H3)2(SiMe2)2}Ru2(CO)4(μ-H)]+ with Nucleophiles

Complex [{(η 5-C5H3)2(SiMe2)2}Ru2(CO)4(μ-H)]+BF4 - (1H+BF4 -), which features a protonated Ru−Ru bond, reacts with F- to give (η 5-C5H5)2Ru2(CO)4 (2), resulting from the cleavage of both SiMe2 groups, with I- to give the Ru−Ru cleaved product {(η 5-C5H3)2(SiMe2)2}Ru2(CO)4(H)(I) (3), and with phosphines (PEt3, PMe2Ph) to give [{(η 5-C5H3)2(SiMe2)2}Ru2(CO)4(H)(PR3)]+ (4a−b). Reaction of 1H+BF4 - and NaOMe in THF generates {(η 5-C5H4)2SiMe2}Ru2(CO)4 (5), resulting from the cleavage of a single SiMe2 group, while the reaction of 1H+BF4 - and NaOMe in MeOH generates {μ-η 5:η 5-(C5H3SiMe2OMe)(C5H4)SiMe2}Ru2(CO)4 (6), resulting from the partial cleavage of a SiMe2 group. Reaction of 1H+BF4 - and NaSR (R = Me, Et) in THF generates {(η 5-C5H3)2(SiMe2)2}Ru2(CO)4(H)(SR) (R = Me, Et; 7a−b), which undergoes rearrangement upon contact with neutral and basic alumina or silica to give complexes {μ-η 5:η 1:η 5-(C5H3CO)(C5H4)(SiMe2)2O}Ru2(μ-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.