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, Merzweiler, Kurt, Rheinwald, Gerd, Stoeckli-Evans, Helen, Süss-Fink, Georg

The electron-deficient cluster (mu(2)-H)Ru-3(CO)(9)[mu(3)-NS(O)MePh] (1) reacts with the terminal alkyne PhCH2C=CH to give the vinyl complex Ru-3(mu(2)-CO)(2)(CO)(6)[mu(3)-NS(O)MePh](mu(2)-eta(1),eta(2)-PhCH2C=CH2 ) (2). The analogous reaction with internal alkynes (RC=CR') affords the clusters Ru-3(mu(2)-CO)(CO)(7)[mu(3)-NS(O)MePh](mu(3)-eta(1),eta(2)-RC=CHR') (3: R = R' = Pr "; 4: R = Ph; R' = Bu ") in which the vinyl ligand has opened a Ru-Ru bond upon coordination the Ru-3 framework. In the case of diphenylacetylene, reaction with two equivalents of the alkyne, yields the vinyl-alkyne cluster (mu(2)-H)Ru-3(CO)(6)(mu(2)-eta(1),eta(2)-PhC=CHPh)(mu(3)-eta(1),eta(2)-P hC=CPh)[mu(3)-eta(1),eta(2)-NS(O)Me(C6H4)] (5) with ortho-metallation of the phenyl substituent of the sulfoximido cap. (C) 1997 Elsevier Science S.A.