Stoeckli-Evans, Helen

2000, Süss-Fink, Georg, Plasseraud, Laurent, Maisse-Francois, Aline, Stoeckli-Evans, Helen, Berke, Heinz, Fox, Thomas, Gautier, Régis, Saillard, Jean-Yves

A low-temperature H-1-NMR study suggests the tetranuclear cluster dication [H6Ru4(C6H6)(4)](2+) (1) to contain an H-2 ligand that undergoes, upon warming of the solution, an intramolecular exchange with the four hydride ligands at the Ru-4 framework. Whereas two of the three NMR signals at - 120 degrees C in the hydride region show T-1 values in the range 200-300 ms, the least deshielded resonance at delta = - 17.33 ppm exhibits a T-1 value of only 34 ms, characteristic of an H-2 ligand. a re-examination of the single-crystal X-ray structure analysis of the chloride salt of 1 supports this interpretation by a short distance of 1.14(0.15) Angstrom between two hydrogen atoms coordinated as a PI-PI ligand in a side-on fashion to one of the triangular faces of the Ru-4 tetrahedron. The distance between one of the two hydrogen atoms of the H-2 ligand and one of the four hydride ligands is also very short [1.33(0.15) Angstrom], suggesting an additional H-2... H interaction. The presence of this H-3, unit over one of the three Ru-3 faces in 1 may explain the deformation of the Ru-4 skeleton from the expected tetrahedral symmetry. Density functional theory (DFT) calculations on 1 indicate a very soft potential energy surface associated with the respective displacement of the three interacting cofacial hydrogen atoms. In accordance with these results, the cluster dication 1 tends to loose molecular hydrogen to form the cluster dication [H4Ru4(C6H6)(4)](2+) (2). The equilibrium between 1 and 2 can be used for catalytic hydrogenation reactions. (C) 2000 Elsevier Science S.A. All rights reserved.

1999, Ferrand, Vincent, Süss-Fink, Georg, Neels, Antonia, Stoeckli-Evans, Helen

The tetrahedral cluster anion [Ru3Ir(CO)(13)](-) (1) reacts with internal alkynes RC=CR' to afford the alkyne derivatives [Ru3Ir(CO)(11) (RCCR')](-) (2: R = R' = Ph; 3: R = R' = Et; 4: R = Ph; R' = Me; 5: R = R' = Me) which have a butterfly arrangement of the Ru,Ir skeleton in which the alkyne is coordinated in mu(4)-eta(2) fashion. Under CO pressure they undergo fragmentation to give the trinuclear cluster anions [Ru2Ir(CO)(9)(RCCR')](-) (6: R = R' = Ph; 7: R = R' = Et; 8: R = Ph; R' = Me; 9: R = R' = Me), in which the alkyne ligand is coordinated in a mu(3)-eta(2) parallel fashion. Protonation of these trinuclear anions leads to the formation of the corresponding neutral hydride clusters [HRu2Ir(Co)(9)(RC=CR')] (10: R = R' = Ph; 11: R = R' = Et; 12: R = Ph; R' = Me; 13: R = R' = Me). The protonation of the butterfly anions 2 and 3, however, gives rise to the formation of the neutral tetrahedral clusters [HRu3Ir(CO)(11)(RCCR')] (14: R = R' = Ph and 15: R = R' = Et), respectively. The analogous clusters [HRu3Ir(CO)(11)(PhCCCH3)] (16) and [HRu3Ir(CO)(11)(CH3CCCH3)] (17) are only accessible from the reaction of the neutral cluster [HRu3Ir(CO)(13)] with the corresponding alkynes. The complexes 2, 4, 5, 6, 10, 12 and 15 are characterised by Xray structure analysis.