116698-72-7Relevant academic research and scientific papers
Synthesis and reactivity of [PPh4][MRu3Cp(CO)12] clusters (M = Mo, W)
Cazanoue, Martine,Lugan, No?l,Bonnet, Jean-Jacques,Mathieu, René
, p. 2480 - 2486 (2008/10/08)
The clusters [PPh4][MRu3Cp(CO)12] (1a, M = Mo; 1b, M = W) have been synthesized in 70-75% yield by the reaction of [PPh4][MCp(CO)3] with Ru3(CO)12 in boiling THF. The structure of 1a has been established: monoclinic; space group C2h5-P21/c; a = 12.427 (2) ?, b = 13.637 (4) ?, c = 23.811 (4) ?; β = 86.02 (1)°; Z = 4. The reactivity of 1a,b toward H+, H2, and alkynes has been studied. The unstable complexes (μ-H)MRu3Cp(CO)12 (2a, M = Mo; 2b, M = W) have been obtained by protonation. Molecular hydrogen reacts with 1a,b in boiling THF to give [PPh4][(μ-H)2MRu3Cp(CO)11] (3a, M = Mo; 3b, M = W) in good yield. They are fluxional on the NMR time scale. The alkynes MeC≡CMe or PhC≡CH react with 1a,b in boiling THF to give respectively [PPh4][MRu3Cp(CO)10(μ4-η 2-MeC≡CMe)] (4a, M = Mo; 4b, M = W) and [PPh4][MRu3Cp(CO)10(μ4-η 2-PhC≡CH)] (5a, M = Mo; 5b, M = W). The structure of 4b has been determined at -150°C: triclinic; space group Ci1-P1; a = 14.035 (2) ?, b = 14.818 (5) ?, c = 10.311 (3) ?; α = 98.70 (3)°, β = 108.48 (3)°, γ = 86.65 (2)°; Z = 2. It consists of a butterfly arrangement of metal atoms, the tungsten atom being on the hinge and the alkyne being μ4-η2 bonded. Compounds 3a,b react also with an excess of the same alkynes affording respectively 4a,b and 5a,b and the corresponding alkenes.
