The mixed-metal carbonyl cluster anion [Ru3Ir(CO)13]−: synthesis, molecular structure, fluxionality, reactivity †

Süß‐Fink, Georg; Haak, Susanne; Ferrand, Vincent; Stœckli-Evans, Helen

doi:10.1039/a704657j

Cited by 27 publications

(46 citation statements)

References 16 publications

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“…[4,8,9] In the three clusters, the coordination of the eleven carbonyl ligands is the same: While nine carbonyl groups are terminal, one CO ligand [C(6)O (6) C(14)ϪRu(3) ϭ 2.8115(3) Å ; 5: C(15)ϪRu(3) ϭ 2.8613(7) tron count of 60e is consistent with Wade's rules which predict a closo structure. [15] Å ].…”

Section: (Rccrј)]supporting

confidence: 77%

“…[20,22a,22c,23a] thermal ellipsoids are drawn at 50% of propability 45:55. This ratio does not change down to Ϫ58°C (CDCl 3 ), Molecular Structure of [Ru 2 Ir(CO) 9 …”

Section: (Rccrј)]mentioning

confidence: 82%

“…Ϫ [9] with internal alkynes, which af-2.82 is observed for the methyl group, indicating the presfords anionic alkyne clusters of the type [Ru 3 Ir-ence of only one isomer. In the case of 3 and 5 (containing (CO) 11 …”

Section: [Ru 3 Ir(co) 11 (Rccrј)] ؊ (2؊5)mentioning

confidence: 87%

“…[4] 1). The 1 H-NMR spectra of 2Ϫ5 are complicated by the In a recent publication, [8] we have described the reactivity multiplets of the [N(PPh 3 ) 2 ] ϩ cation; for 2 and 4, the resonof the neutral tetrahedral cluster [HRu 3 Ir(CO) 13 ] [9] towards ances of the phenyl protons of the alkyne ligands overlap alkynes and its catalytic potential in hydrogenation reac-with the signals of the cation. In the case of 4 (containing tions.…”

Section: [Ru 3 Ir(co) 11 (Rccrј)] ؊ (2؊5)mentioning

confidence: 98%

“…The carbonϪcarbon bond is closer to Ru(1) than to Ru(3) in the three clusters, the torsion angle between the can release a "Co(CO)" fragment to give the trinuclear complex [RuCo 2 (CO) 9 (µ 3 -η 2 -C 2 Ph 2 )] in which the alkyne carbonϪcarbon backbone and the Ir(1)ϪRu(2) edge is close to 0°[2: 0.0°(18); 4: Ϫ0.04(11); 5: 0.3°(2)] indicating adopts a parallel coordination.…”

Section: (Rccrј)]mentioning

confidence: 99%

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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

Süß‐Fink

Neels

et al. 1999

Eur. J. Inorg. Chem.

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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 Ru3Ir skeleton in which the alkyne is coordinated in a μ4‐η2 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 μ3‐η2 parallel fashion. Protonation of these trinuclear anions leads to the formation of the corresponding neutral hydrido 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 X‐ray structure analysis.

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Section: (Rccrј)]supporting

confidence: 77%

“…[20,22a,22c,23a] thermal ellipsoids are drawn at 50% of propability 45:55. This ratio does not change down to Ϫ58°C (CDCl 3 ), Molecular Structure of [Ru 2 Ir(CO) 9 …”

Section: (Rccrј)]mentioning

confidence: 82%

Section: [Ru 3 Ir(co) 11 (Rccrј)] ؊ (2؊5)mentioning

confidence: 87%

Section: [Ru 3 Ir(co) 11 (Rccrј)] ؊ (2؊5)mentioning

confidence: 98%

Section: (Rccrј)]mentioning

confidence: 99%

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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

Süß‐Fink

Neels

et al. 1999

Eur. J. Inorg. Chem.

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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

Süß‐Fink²,

Neels

et al. 1999

Eur. J. Inorg. Chem.

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The tetrahedral cluster anion [Ru 3 Ir(CO) 13 ] -(1) reacts with neutral hydrido clusters [HRu 2 Ir(CO) 9 (RCϵCRЈ)] (10: R = RЈ = Ph; 11: R = RЈ = Et; 12: R = Ph; RЈ = Me; 13: R = RЈ = Me). internal alkynes RCϵCRЈ to afford the alkyne derivatives [Ru 3 Ir(CO) 11 (RCCRЈ)] -(2: R = RЈ = Ph; 3: R = RЈ = Et; 4: R = The protonation of the butterfly anions 2 and 3, however, gives rise to the formation of the neutral tetrahedral clusters Ph; RЈ = Me; 5: R = RЈ = Me) which have a butterfly arrangement of the Ru 3 Ir skeleton in which the alkyne is [HRu 3 Ir(CO) 11 (RCCRЈ)] (14: R = RЈ = Ph and 15: R = RЈ = Et), respectively. The analogous clusters [HRu 3 Ir(CO) 11 -coordinated in a µ 4 -η 2 fashion. Under CO pressure they undergo fragmentation to give the trinuclear cluster anions (PhCCCH 3 )] (16) and [HRu 3 Ir(CO) 11 (CH 3 CCCH 3 )] (17) are only accessible from the reaction of the neutral cluster [Ru 2 Ir(CO) 9 (RCCRЈ)] -(6: R = RЈ = Ph; 7: R = RЈ = Et; 8: R = Ph; RЈ = Me; 9: R = RЈ = Me), in which the alkyne ligand is [HRu 3 Ir(CO) 13 ]with the corresponding alkynes. The complexes 2, 4, 5, 6, 10, 12 and 15 are characterised by X-coordinated in a µ 3 -η 2 parallel fashion. Protonation of these trinuclear anions leads to the formation of the corresponding ray structure analysis.

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Metal Carbonyls

McIndoe

Dyson

2003

Kirk-Othmer Encyclopedia of Chemical Technology

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Carbon monoxide forms a host of metal carbonyl complexes, at least one for every transition metal. Mononuclear, polynuclear, and heteronuclear metal carbonyls are all known. The complexes, of general formula M x (CO) y , may be charged or neutral; the metal or metals are in low, zero, or negative oxidation states. Synthesis of the metal carbonyls usually proceeds either from the reduction of the corresponding metal salt, although direct reaction between the metal and CO takes place for certain elements. Clusters are usually made via condensation of lower molecular weight compounds. The structure and bonding of the metal carbonyls, including those of cluster compounds, follow well‐defined rules. Metal carbonyls are extremely useful as reagents in organic synthesis and catalysts, playing a pivotal role in both the Reppe and the oxo processes, as well as in the preparation of fine chemicals.

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The mixed-metal carbonyl cluster anion [Ru3Ir(CO)13]−: synthesis, molecular structure, fluxionality, reactivity †

Cited by 27 publications

References 16 publications

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′)]

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′)]

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′)]

Metal Carbonyls

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