Reactions of the Tetrahedral Clusters [MCo3(CO)12]-(M = Ru, Fe) with Functional Mono- and Diynes

Choualeb, Aldjia; Braunstein, Pierre; Rosé, Jacky; Welter, Richard

doi:10.1021/ic034832k

Cited by 25 publications

(21 citation statements)

References 45 publications

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“…The multiplet between δ = 7.00 and 7.77 ppm is due to aromatic protons, the singlet at δ = 1.82 ppm can be assigned to Cp* methyl protons, and the singlet at δ = 10.58 ppm corresponds to the alkyne C-H. The MS is also consistent with structures like those observed for 2g 2 and 2g 3 . Based on these spectroscopic characteristics it was thus tentatively identified as a third isomer in which the alkyne CϵC bond is parallel to an Ru-Ir hinge, and the bulkier Ph group of the alkyne is trans to the Cp*Ir, i.e., similar to 2c-f. Figure 7.…”

Section: Resultssupporting

confidence: 73%

“…The major product, obtained in 28 % yield, was identified as [Cp*IrRu 3 (CO) 9 (PhCCH)] (2g 3) ; it has been characterised spectroscopically and analytically, as well as by a singlecrystal X-ray structure analysis. The ORTEP plot of 2g 3 is shown in Figure 7, and it shows that the alkyne CϵC bond is parallel to an Ru-Ru hinge. The other two products were obtained in very low yields.…”

Section: Resultsmentioning

confidence: 99%

“…The other two products were obtained in very low yields. A single-crystal X-ray structural study on 2g 2 showed it to be a hinge-apex isomer of 2g 3 in which the bulkier Ph group of the alkyne is oriented cis to the Cp*Ir; the ORTEP plot for 2g 2 is shown in Figure 8. The IR spectrum of the third product, 2g 1 , shows a pattern similar to that of 2a-f.…”

Section: Resultsmentioning

confidence: 99%

“…Based on these spectroscopic characteristics it was thus tentatively identified as a third isomer in which the alkyne CϵC bond is parallel to an Ru-Ir hinge, and the bulkier Ph group of the alkyne is trans to the Cp*Ir, i.e., similar to 2c-f. Figure 7. ORTEP diagram of 2g 3 . Thermal ellipsoids are drawn at 50 % probability level.…”

Section: Resultsmentioning

confidence: 99%

“…[3] The reaction of tetrahedral clusters with alkynes often results in cluster opening to give "butterfly" structures, [4] where the M 3 MЈ skeleton takes the form of a butterfly and the alkyne C 2 unit binds to the metal framework in a μ 4 -η 2 fashion to form a quasi-octahedral M 3 MЈC 2 skeleton. [5] The total electron count for these clusters are best considered using the Wade's system, i.e., as octahedral M 3 MЈC 2 clusters, with each CR unit donating three electrons to the skeletal bonding.…”

Section: Introductionmentioning

confidence: 99%

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Reaction of the Heteronuclear Cluster [Cp*IrRu₃(μ‐H)₂(CO)₁₀] with Alkynes: Stereoselective Binding

Srinivasan

Leong

2006

Eur J Inorg Chem

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The reaction of the heteronuclear cluster [Cp*IrRu3(μ‐H)2(CO)10] (1) with the symmetrical alkynes RCCR (R = Ph, Et) afforded the butterfly clusters [Cp*IrRu3(CO)9(RCCR)] (2) and the trinuclear clusters [Cp*IrRu2(CO)7(RCCR)] (3) and [Ru3(CO)8(C4R4)] (4). The clusters 2 and 3 have the alkyne aligned parallel to an Ru–Ir bond. The reaction of 1 with unsymmetrical alkynes also afforded stereoselective binding of the alkyne such that the bulkier substituent was pointing away from the Cp*Ir moiety; with PhCCH, however, all three stereoisomers were obtained. With the bis‐silylated alkynes (R = SiMe3, SiEt3), loss of one trialkylsilyl group occurred to give [Cp*IrRu3(CO)9(HCCR)] and [Ru3(CO)9(μ‐H)(CCR)] (5). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Section: Resultssupporting

confidence: 73%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Reaction of the Heteronuclear Cluster [Cp*IrRu₃(μ‐H)₂(CO)₁₀] with Alkynes: Stereoselective Binding

Srinivasan

Leong

2006

Eur J Inorg Chem

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Site Selectivity in the Reactions of the Hexanuclear Platinum Cluster [Pt₆(μ‐PtBu₂)₄(CO)₆][CF₃SO₃]₂

Bonaccorsi

Biani

Leoni

et al. 2008

Chemistry A European J

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The previously reported hexanuclear cluster [Pt(6)(mu-PtBu(2))(4)(CO)(6)](2+)[Y](2) (1-Y(2): Y=CF(3)SO(3) (-)) contains a central Pt(4) tetrahedron bridged at each of the opposite edges by another platinum atom; in turn, four phosphido ligands bridge the four Pt-Pt bonds not involved in the tetrahedron, and, finally, one carbonyl ligand is terminally bonded to each metal centre. Interestingly, the two outer carbonyls are more easily substituted or attacked by nucleophiles than the inner four, which are bonded to the tetrahedron vertices. In fact, the reaction of 1-Y(2) with 1 equiv of [nBu(4)N]Cl or with an excess of halide salts gives the monochloride [Pt(6)(mu-PtBu(2))(4)(CO)(5)Cl](+)[Y], 2-Y, or the neutral dihalide derivatives [Pt(6)(mu-PtBu(2))(4)(CO)(4)X(2)] (3: X=Cl; 4: X=Br; 5: X=I). Moreover, the useful unsymmetrically substituted [Pt(6)(mu-PtBu(2))(4)(CO)(4)ICl] (6) was obtained by reacting equimolar amounts of 2 and [nBu(4)N]I, and the dicationic derivatives [Pt(6)(mu-PtBu(2))(4)(CO)(4)L(2)](2+)[Y](2) (7-Y(2): L=(13)CO; 8-Y(2): L=CNtBu; 9-Y(2): L=PMe(3)) were obtained by reaction of an excess of the ligand L with 1-Y(2). Weaker nitrogen ligands were introduced by dissolving the dichloride 3 in acetonitrile or pyridyne in the presence of TlPF(6) to afford [Pt(6)(mu-PtBu(2))(4) (CO)(4)L(2)](2+)[Z](2) (Z=PF(6) (-), 10-Z(2): L=MeCN; 11-Z(2): L=Py). The "apical" carbonyls in 1-Y(2) are also prone to nucleophilic addition (Nu(-): H(-), MeO(-)) affording the acyl derivatives [Pt(6)(mu-PtBu(2))(4)(CO)(4)(CONu)(2)] (12: Nu=H; 13: Nu=OMe). Complex 12 is slowly converted into the dihydride [Pt(6)(mu-PtBu(2))(4)(CO)(4)H(2)] (14), which was more cleanly prepared by reacting 3 with NaBH(4). In a unique case we observed a reaction involving also the inner carbonyls of complex 1, that is, in the reaction with a large excess of the isocyanides R-NC, which form the corresponding persubstituted derivatives [Pt(6)(mu-tPBu(2))(4)(CN-R)(6)](2+)[Y](2), (15-Y(2): R=tBu; 16-Y(2) (2-): R=-C(6)H(4)-4-C triple bond CH). All complexes were characterized by microanalysis, IR and multinuclear NMR spectroscopy. The crystal and molecular structures of complexes 3, 5, 6 and 9-Y(2) are also reported. From the redox viewpoint, all complexes display two reversible one-electron reduction steps, the location of which depends both upon the electronic effects of the substituents, and the overall charge of the original complex.

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Organo‐Transition‐Metal Cluster Complexes

Humphrey

Cifuentes

2004

ChemInform

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This chapter covers the chemistry of metal carbonyl and organometallic clusters containing three or more metal atoms. The treatment is in Periodic Group order, homometallic compounds being followed by heterometallic clusters. Ligands are not shown for high-nuclearity clusters, emphasis being placed on core geometry. 2 Spectroscopic studies The first gas-phase infrared spectra of a range of anionic iron clusters ([Fe 3 (CO) 10 ] À to [Fe 5 (CO) 14 ] À) have been reported. Spectral data of this type were combined with DFT calculations for smaller complexes ([Fe(CO) 4 ] À , [Fe 2 (CO) 7 ] À , [Fe 2 (CO) 8 ] À) to obtain structural information for the cluster anions. 1 Spectroelectrochemical and computational studies on the reversible two-electron reduction of bis(alkynyl) clusters Ru 4 (m 4-Z 2-RC 2 R) 2 (m-CO)(CO) 10 show the first-formed product, which contains a square-planar metal core with the alkyne ligands coordinated to opposite faces, quickly isomerizes to a thermodynamically more stable product where the alkyne ligands lie parallel to each other across the metal framework. 2 Quantitative IR analysis of Rh 4 (m-CO) 3 (CO) 9 , combined with deconvolution techniques, has been used to obtain a spectrum of the all-terminal CO complex Rh 4 (CO) 12 , even though it constitutes only ca. 1% of the sample. 3 Laser desorption time-of-flight mass spectrometry affords the best results for anionic clusters when they are examined in the absence of matrix, the parent ion being observed in the majority of cases. In contrast, the spectra of neutral clusters show high-mass cluster aggregation and decarbonylation, with the CO:M ratio dropping with increasing cluster size, suggesting a metal-core rearrangement. 4 A picosecond time-resolved UV/Vis and IR spectroscopic study of the photolysis of Os 3 (CO) 10 (s-cis-cyclohexa-1,3-diene), combined with DFT calculations on the geometry-optimized Os 3 (CO) 10 (buta-1,3-diene), indicates products result from stepwise formation of two bridging carbonyl ligands, with each intermediate containing a cleaved Os-Os bond bridged by the 1,3-diene ligand. 5 Similar comparisons of the photochemical reactivity of the diimine clusters Os 3 (CO) 10 (Z-L) (L = [AcPy-MV] 2+ , Pr i-AcPy, 1) show that irradiation of the methyl viologen cluster results in transfer of a cluster-core electron to the lowest p * orbital of the MV 2+ unit, resulting in formation of a charge-separated state that is stable in acetonitrile, but either decays to regenerate the starting cluster (88%) or forms stable open-core biradicals (12%) in acetone. Electrochemical reduction of the viologen cluster decreases the electron-accepting characteristics of the ligand such that irradiation results in formation of zwitterions analogous to those observed from the irradiation of related non-substituted Os 3 (CO) 10 (a-diimine) clusters. 6 The related mixed-metal cluster RuOs 2 (CO) 10 (Pr i-AcPy) contains the diimine ligand coordinated to the ruthenium atom and also produces biradical products on irradiation in weakly coordinating so...

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Reactions of the Tetrahedral Clusters [MCo₃(CO)₁₂]^-(M = Ru, Fe) with Functional Mono- and Diynes

Cited by 25 publications

References 45 publications

Reaction of the Heteronuclear Cluster [Cp*IrRu₃(μ‐H)₂(CO)₁₀] with Alkynes: Stereoselective Binding

Reaction of the Heteronuclear Cluster [Cp*IrRu₃(μ‐H)₂(CO)₁₀] with Alkynes: Stereoselective Binding

Site Selectivity in the Reactions of the Hexanuclear Platinum Cluster [Pt₆(μ‐PtBu₂)₄(CO)₆][CF₃SO₃]₂

Organo‐Transition‐Metal Cluster Complexes

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Reactions of the Tetrahedral Clusters [MCo3(CO)12]-(M = Ru, Fe) with Functional Mono- and Diynes

Cited by 25 publications

References 45 publications

Reaction of the Heteronuclear Cluster [Cp*IrRu3(μ‐H)2(CO)10] with Alkynes: Stereoselective Binding

Reaction of the Heteronuclear Cluster [Cp*IrRu3(μ‐H)2(CO)10] with Alkynes: Stereoselective Binding

Site Selectivity in the Reactions of the Hexanuclear Platinum Cluster [Pt6(μ‐PtBu2)4(CO)6][CF3SO3]2

Organo‐Transition‐Metal Cluster Complexes

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Reactions of the Tetrahedral Clusters [MCo₃(CO)₁₂]^-(M = Ru, Fe) with Functional Mono- and Diynes

Reaction of the Heteronuclear Cluster [Cp*IrRu₃(μ‐H)₂(CO)₁₀] with Alkynes: Stereoselective Binding

Reaction of the Heteronuclear Cluster [Cp*IrRu₃(μ‐H)₂(CO)₁₀] with Alkynes: Stereoselective Binding

Site Selectivity in the Reactions of the Hexanuclear Platinum Cluster [Pt₆(μ‐PtBu₂)₄(CO)₆][CF₃SO₃]₂