Stoeckli-Evans, Helen

2001, Faure, Matthieu, Onidi, Anne, Neels, Antonia, Stoeckli-Evans, Helen, Süss-Fink, Georg

The dinuclear cation [(eta (5)-C5Me5)(2)Ir2(mu (2)-H)(3)](+) (1) reacts in aqueous solution with pyrazole and 4-methylpyrazole to give the bispyrazolato complexes [(eta (5)-C5Me5)(2)Ir-2(mu (2)-H)(mu (2)-eta (1),eta (1)-N2C3H2R)(2)](+) (R = H, 2; R = Me, 3). The reaction of complex 1 with 1,2,4-triazole results in the formation of the bistriazolato complex [(mu (5)-C5Me5)(2)Ir-2(mu (2)-H)(mu (2)-eta (1),eta (1)-N3C2H2)(2)](+) (4). Successive protonation of the triazolato ligands in 4 leads to the complexes [(eta (5)-C5Me5)(2)Ir-2(mu (2)-H)(mu (2)-eta (1),eta (1)-N3C2H2)(mu (2)-eta (1),eta (1)-N3C2H3)](2+) (5) and [(eta (5)-C5Me5)(2)Ir-2(mu (2)-H)(mu (2)-eta (1),eta (1)-H3C2H3)(2)](3+) (6). The reaction of 1 with 1,2,3-triazole gives a 1:1 mixture of the bistriazolato complexes [(eta (5)-C5Me5)(2)Ir-2(mu (2)-H)(mu (2)-eta (1),eta (1)-N3C2H2)(2)](+) with parallel (7a) and antiparallel (7b) coordination of the triazolato ligands. The X-ray structure analysis of 3 reveals a diiridium backbone which is bridged by two pyrazolato ligands, the N-N axis being coordinated in a mu (2)-eta (1),eta (1) fashion. (C) 2001 Elsevier Science B.V. All rights reserved.

1998, Jahncke, Manfred, Neels, Antonia, Stoeckli-Evans, Helen, Süss-Fink, Georg

The dinuclear cation [(eta(6)-C6Me6)(2)Ru-2(mu(2)-H)(3)](+) (1) reacts in aqueous solution with pyrazole and 4-methylpyrazole to give the bispyrazolato complexes [(eta(6)-C6Me6)(2)Ru-2(mu(2)-H)(mu(2)-eta(1),eta(1)-N2C3H2R)(2)](+) (R = H: 2, R = Me: 3). The reaction with 1,2,4-triazole results in the formation of the bistriazolato complex [(eta(6)-C6Me6)(2)Ru-2(mu(2)-H)(mu(2)-eta(1),eta(1)-N3C2H2)(2)](+) (4) Successive protonation of the triazolato ligands in 4 leads to the complexes [(eta(6)-C6Me6)(2)Ru-2(mu(2)-H)(mu(2)-eta(1),-N3C2H2)(mu(2)-eta(1),eta(1 )-N3C2H3)](2+) (5) and [(eta(6)-C6Me6)(2)RU2(mu(2)-H)(mu(2)-eta(1),eta(1)-N3C2H2)(2)](3+) (6). The reaction of 1 with 1,2,3-triazole gives a 1:1 mixture of the bistriazolato complexes [(eta(6)-C6Me6)(2)Ru-2(mu(2)-H)(mu(2)-eta(1),eta(1)-N3C2H2)(2)](+) with parallel (7a) and anti-parallel (7b) coordination of the triazolato ligands. The single-crystal X-ray structure analyses of 2 (hexafluorophosphate salt) and 4 (tosylate salt) reveal for both complex types a ruthenium-ruthenium backbone being bridged by the two heterocyclic ligands with the N-N axis coordinated in a mu(2)-eta(1),eta(1)-fashion. A single-crystal X-ray structure analysis of title complex 1 (hexafluorophosphate salt) confirms the presence of three bridging hydride ligands with a Ru-Ru distance of only 2.47 Angstrom. (C) 1998 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.

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.

1999, Süss-Fink, Georg, Haak, Susanne, Ferrand, Vincent, Stoeckli-Evans, Helen

The cluster anion [Os3Ir(CO)(13)](-) (1) was prepared in 50% yield by reaction of Os-3(CO)(12) with [Ir(CO)(4)](-). The single-crystal X-ray structure analysis of the bis(triphenylphosphoranylidene)ammonium salt shows 1 to consist of a tetrahedral metal core with one of the 13 carbonyl ligands being bridging. Protonation of 1 led to the neutral cluster HOs3Ir(CO)(13) (2), whereas the hydrogenation gave the cluster anion [H2Os3Ir(CO)(12)](-) (3). The catalytic activity of 1 for the carbonylation of methanol was studied. Using CH3I as co-catalyst, catalytic turnover numbers up to 1800 were obtained (140 degrees C, 30 bar) within 14 h. (C) 1999 Elsevier Science B.V. All rights reserved.