Reactivity of a Triruthenium Cluster Complex Containing a μ<sub>3</sub>-η<sup>3</sup>(<i>C</i>,<i>N</i><sub>2</sub>) Ligand Derived from 2-Amino-7,8-benzoquinoline. Coupling of This Ligand with C<sub>3</sub> Fragments and Characterization of μ<sub>3</sub>-Vinylidene and μ-Stannylene Derivatives
收藏资源简介：
The reactivity of the triruthenium cluster complex [Ru3(μ3-η3(C,N2)-Habq)(CO)9] (1; H2abqH = 2-amino-7,8-benzoquinoline) with alkynes, tetrafluoroboric acid, dihydrogen, and tertiary silanes and stannanes is reported. The compounds [Ru3(μ3-η3(C,N2)-Habq)(μ3-η2-CCHR)(CO)8] (R = Ph (2), p-tolyl (3), Bu (4), CMe2OH (5), CPh2OH (6), c-C5H8OH (7)), which contain a face-capping vinylidene ligand, have been prepared by treating complex 1 with the corresponding terminal alkynes. However, the reaction of complex 1 with propargyl alcohol leads to [Ru3(μ3-η5(C3,N2)-HabqCHCHCH2)(μ-CO)2(CO)6] (8), which bears a new ligand that contains an allylic C3 fragment attached to the C10 carbon atom of the original Habq ligand. Two compounds have been isolated from the reaction of complex 1 with 1-(trimethylsilyl)penta-1,4-diyne, [Ru3(μ3-η3(C,N2)-Habq)(μ3-η2-CCHCH2CCSiMe3)(CO)8] (9) and Ru3(μ3-η5(C3,N2)-HabqCHCHCH2)(μ-CO)2(CO)6] (10). While compound 9 is a vinylidene derivative, analogous to 2−7, compound 10 contains an allylated Habq ligand analogous to 8. The reactions of 1 with internal alkynes lead to mixtures of [Ru3(μ3-η3(C,N2)-Habq)2(μ-CO)(CO)6] (11) and known alkyne-containing ruthenium compounds. Protonation of 1 with tetrafluoroboric acid gives the cationic hydride [Ru3(μ-H)(μ3-η3(C,N2)-Habq)(CO)9][BF4] (12). Free H2abqH and [Ru4(μ-H)4(CO)12] are formed when complex 1 is treated with hydrogen (1 atm, 20 °C). At room temperature, complex 1 does not react with tertiary silanes but reacts with tertiary stannanes to give [Ru3(μ-H)(μ3-η3-Habq-C,N,N)(SnR3)(CO)8] (R = Ph (13), Bu (14)). These compounds slowly release HR at room temperature to render the derivatives [Ru3(μ3-η3(C,N,N)-Habq)(μ-SnR2)(μ-CO)(CO)7] (R = Ph (15), Bu (16)), which contain a bridging stannylene ligand. All this reactivity is quite different from that known for neutral hydrido triruthenium carbonyl clusters containing face-capping N-heterocyclic ligands.
