Reactivity of ruthenium trihydrides with Broensted and Lewis acids. X-ray crystal structures of {Cp*Ru[C6H9P(C6H11)2]}BF4 and {{Cp*RuH[P(C6H11)3]}(.mu.-H)2Cu(.mu.-Cl)}2. Evidence for exchange coupling between two hydrogen atoms

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The reaction of Cp*RuH 3 (PPh 3 ) (1a; Cp*=C 5 Me 5 ) with P(OMe) 3 produces Cp*RuH(PPh 3 )[P(OMe) 3 ] (2), whereas no reaction occurs between 1a and pyridine. The protonation of 1a by HBF 4 /Et 2 O yields [Cp*RuH 2 (PPh 3 ) 2 ]BF 4 (3), but the same reaction with Cp*RuH 3 [P(c-C 6 H 11 ) 3 ] (1b) leads to the evolution of 3 mol of H 2 and formation of {Cp*Ru[C 6 H 9 P(c-C 6 H 11 ) 2 ]}BF 4 (4). Complex 4 contains a cyclohexenyl group coordinated through the C=C double bond and a strong agostic interaction, as demonstrated by both and X-ray crystal structure determination and 1 H and 13 C NMR studies. The protonation of 1b with CF 3 COOH produces Cp*Ru(OCOCF 3 [P(c-C 6 H 11 ) 3 ] (5), in which the trifluoroacetato group is bidentate. The reactions of 1b with the Lewis acids [CuCl] n and [Cu(MeCN) 4 ]BF 6 lead to {[Cp*Ru[P(c-C 6 H 11 ) 3 ]H-(μ-H) 2 ]Cu(μ-Cl)} 2 (6), which was characterized by X-ray crystallography, and to {[Cp*Ru[P(c-C 6 H 11 ) 3 ]H-(μ-H) 2 ] 2 Cu}PF 6 (7), respectively