Faculté des sciences

Tri- and Tetranuclear Mixed-Metal Clusters Containing Alkyne Ligands : Synthesis and Structure of [Ru3Ir(CO)11(RCCR’)]-, [Ru2Ir(CO)9(RCCR’)]-, and [HRu2Ir(CO)9(RCCR’)]

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

In: European Journal of Inorganic Chemistry, 1999, vol. 5, p. 853 - 862

The tetrahedral cluster anion [Ru3Ir(CO)13]- (1) reacts with internal alkynes RCCR 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 Ru3Ir skeleton in which the... Plus

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    Summary
    The tetrahedral cluster anion [Ru3Ir(CO)13]- (1) reacts with internal alkynes RCCR 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 Ru3Ir skeleton in which the alkyne is coordinated in a μ42 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 μ32 parallel fashion. Protonation of these trinuclear anions leads to the formation of the corresponding neutral hydrido clusters [HRu2Ir(CO)9 (RCCR)] (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 X-ray structure analysis.