Stoeckli-Evans, Helen

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.

1997, Ferrand, Vincent, Gambs, Céline, Derrien, Nadine, Bolm, Carsten, Stoeckli-Evans, Helen, Süss-Fink, Georg

The reaction of the electron-deficient cluster (mu(2)-H)Ru-3(CO)(9)[mu(3)-NS(O)MePh] (1) with para-nitrotolane gives, with coupling of two alkyne units and elimination of the para-nitrophenyl fragment, the trinuclear complexes Ru-3(CO)(9)[mu(3)-eta(3)-PhCCCC(H)Ph][mu(2)-NS(O)MePh] (2) and Ru-3(mu(2)-CO)(CO)(7)[mu(3)-eta(3)-PhCCCC(H)Ph][mu(3)-NS(O)MePh] (3). The resulting organic moiety, coordinated as mu(3)-eta(3)-5e-donor, is best considered as a butenynyl (PhC=C-C=C(H)Ph) ligand in 2 and as a butatrienyl (PhC=C=C=C(H)Ph) ligand in 3. From the reaction mixture, the two isomeric vinyl complexes Ru-3(mu(2)-CO)(2)(CO)(6)[mu(2)-eta(2)-PhC=C(H)(C6H4-p-NO2)][mu(3)-NS(O)M ePh] (4a) and Ru-3(mu(2)-CO)(2)(CO)(6)[mu(2)-eta(2)-(C6H4-P-NO2)-C=C(H)Ph]-[mu(3)-NS(O )MePh] (4b) complexes can also be isolated. (C) 1997 Elsevier Science S.A.