Generation of Oxo−Carbide Clusters from Direct Scission of a Coordinated Carbonyl Ligand:  Molecular Structures of Cp2W2Ru3(CO)13 and Cp*W(O)Cp*WRu3(μ5-C)(CO)11

Treatment of acetylide cluster Cp*WOs 3 (µ-O) 2 (µ-CCPh)(CO) 9 (1), Cp* ) C 5 Me 5 , with diphenylacetylene affords two cluster complexes Cp*W(O)Os 3 (µ-O)(CCPh)(PhC 2 Ph)(CO) 8 (2) and Cp*W(O)Os 3 (µ-O)(CCPhCPhCPh)(CO) 8 (3a) by alkyne coordination and cluster-assisted formation of C-C bonds between acetylide and alkyne, respectively. For the reaction with phenylacetylene, only the coupled product Cp*W(O)Os 3 (µ-O)(CCPhCHCPh)(CO) 8 (3b) is obtained, together with a small amount of Cp*W(O)Os 3 (µ-O)(CCPhCCHPh)(CO) 8 (4).Complex 2 slowly converts to 3a and the complex Cp*W(O)(µ-O)Os 3 (CCPhCPhCPh)(CO) 8 (5a) when heated in toluene, whereas the formation of 4 is believed to pass through a pathway involving an alkyne-to-vinylidene rearrangement. The conversion from complexes 3 to 5 demonstrates a unique skeletal isomerization involving the interchange of a Cp*W(O) 2 unit and one Os(CO) 3 fragment. Experimental SectionGeneral Information and Materials. Infrared spectra were recorded on a Perkin-Elmer 2000 FT-IR spectrometer.

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“…In fact, the relatively short W-O(terminal) distance observed for 5a supports the existence of a strong Wt O multiple bond interaction. 16…”

Section: Discussionmentioning

confidence: 99%

Alkyne−Acetylide Coupling in Cluster Compounds Bearing a Triosmium Carbonyl Os₃(CO)₈ Fragment and a High Oxidation State (C₅Me₅)W(O)₂ Unit

et al. 1998

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“…The generation of the less congested, edge-bridged tetrahedral cluster core also deserves special attention. It can be tracked back to our previous studies on the synthesis of two pentanuclear complexes LWRu 4 (μ 3 -H)(CO) 14 20e and L 2 W 2 Ru 3 (CO) 13 , L = Cp and Cp* . In both cases, the Cp derivatives exhibit the closely packed, trigonal-bipyramidal geometry.…”

Section: Discussionmentioning

confidence: 70%

“…Each cluster complex was separated by thin-layer chromatography on silica gel and was further purified by recrystallization. The first two complexes 2 and 3 were immediately identified by comparing their IR and 1 H NMR data with the authentic samples prepared from the reaction of Ru 3 (CO) 12 and Cp*W(CO) 3 H, and from the condensation of the cluster Cp*WRu 3 (μ-H)(CO) 12 or 2 with Cp*W(CO) 3 H, respectively . This reactivity pattern strongly suggests that the oxo−carbido complex 3 is produced by the prior formation of the cluster Cp*WRu 3 (μ-H)(CO) 12 or 2 , while the latter is generated from a parallel reaction of Cp*W(CO) 3 H with Ru 3 (CO) 12 , and the Ru 3 (CO) 12 existed in the solution is most likely produced from the thermally induced decomposition of 1a .…”

Section: Resultsmentioning

confidence: 98%

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Competitive Acetylide C−C Bond Scission vs Formation of a Quadruply Bridging Carbonyl Ligand. X-ray Crystal Structures of the Two Pentanuclear Clusters Cp₃W₃Ru₂(μ₄-C)(μ₃-CPh)(CO)₉ and Cp₃W₃Ru₂(μ₃-CCBu^t)(CO)₉

Chi

et al. 1997

Organometallics

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Reactions of Cp*WRu 2 (CCPh)(CO) 8 (1a) with excess Cp*W(CO) 3 H, Cp* ) C 5 Me 5 , affords a carbido-alkylidyne cluster Cp* 3 W 3 Ru 2 (µ 4 -C)(µ 3 -CPh)(CO) 9 (5) alone with three byproducts, which are identified as hydride cluster Cp*WRu 3 (µ-H) 3 (CO) 11 (2), vinylidene cluster Cp* 2 W 2 -Ru 2 (CCHPh)(CO) 9 (4), and a pentanuclear oxo-carbido cluster Cp* 2 W 2 (O)Ru 3 (µ 5 -C)(CO) 11 (3). In contrast, the respective condensation using tert-butyl derivative Cp*WRu 2 -(CCBu t )(CO) 8 (1b) gives an acetylide cluster Cp* 3 W 3 Ru 2 (µ 3 -CCBu t )(CO) 9 (6). The X-ray structural determinations of 5 and 6 reveals the existence of an edge-bridged tetrahedral core, in which the butterfly crater is occupied by a µ 4 -carbide in 5 or a quadruply bridging CO ligand in 6. A plausible mechanism leading to the formation of these two cluster compounds is also presented.Transition metal clusters containing unsaturated alkyne or acetylide fragments have been an area of intense investigation due to their unique physical and chemical properties 1,2 and their relevance to the transformation of small hydrocarbyl intermediates on metal surfaces. Much work has been devoted to the development of this chemistry in recent years. For example, Carty and co-workers reported the syntheses and crystal structures of phosphido ruthenium clusters containing multisite bound acetylide ligands. 3 Adams and coworkers focused on the hydrogenation of alkyne on the layer-segregated, face-shared bioctahedral clusters. 4 Other investigations, such as the studies on the ruthenium and osmium clusters 5 and the heterometallic counterparts, 6 all provided substantial knowledge about the bonding and reactivity of cluster-bound alkyne and acetylide ligands.A much less disclosed pattern of reactivity for such complexes is the C-C bond cleavage, which affords two alkylidyne ligands from the coordinated alkynes. 7 Likewise, the related acetylide ligand, which can be envis-aged as a carbide-alkylidyne in certain polynuclear systems, 8 has been observed to convert to the wellseparated carbide and alkylidyne ligands. 9 In this article, we focus on the irreversible acetylide cleavage through the generation of a Ru 2 W 3 mixed-metal cluster, which offers an opportunity to reveal the essence of the acetylide scission vs the competing process involving the generation of the quadruply bridging CO ligand. 10 In addition, this study supplements our previous report on the reversible acetylide cleavage between the parent acetylide cluster CpWRu 2 (CCPh)(CO) 8 and the polynuclear carbido alkylidyne derivatives CpWRu 4 (µ 5 -C)-(µ-CPh)(CO) 12 and CpWRu 5 (µ 6 -C)(µ-CPh)(CO) 14 , which is also promoted by a cluster building reaction. 11

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“…Recently, this chemistry has been extended into the preparation of complexes possessing two μ 4 -CO ligands, as reported in the case of Ru 6 cluster chemistry and its heterometallic domain . In the meantime, reactivity studies have demonstrated that these multisite-bound CO ligands can convert into carbide ligands through cleavage of C−O bond . In this communication, we extend the scope of these investigations, and report the first synthesis of WRu 6 compounds bearing three such uncommon μ 4 -CO ligands and a related cluster compound with two μ 4 -CO ligands, generated from direct hydrogenation.…”

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confidence: 78%

Synthesis of the First Cluster Complexes Bearing Three Quadruply Bridging CO Ligands: X-ray Crystal Structure of [C₅H₃(SiMe₃)₂]WRu₆(μ₃-H)- (CO)₁₈

Chi

Peng

et al. 1997

J. Am. Chem. Soc.

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Generation of Oxo−Carbide Clusters from Direct Scission of a Coordinated Carbonyl Ligand: Molecular Structures of Cp₂W₂Ru₃(CO)₁₃ and CpW(O)CpWRu₃(μ₅-C)(CO)₁₁

Cited by 28 publications

References 41 publications

Alkyne−Acetylide Coupling in Cluster Compounds Bearing a Triosmium Carbonyl Os₃(CO)₈ Fragment and a High Oxidation State (C₅Me₅)W(O)₂ Unit

Alkyne−Acetylide Coupling in Cluster Compounds Bearing a Triosmium Carbonyl Os₃(CO)₈ Fragment and a High Oxidation State (C₅Me₅)W(O)₂ Unit

Competitive Acetylide C−C Bond Scission vs Formation of a Quadruply Bridging Carbonyl Ligand. X-ray Crystal Structures of the Two Pentanuclear Clusters Cp₃W₃Ru₂(μ₄-C)(μ₃-CPh)(CO)₉ and Cp₃W₃Ru₂(μ₃-CCBu^t)(CO)₉

Synthesis of the First Cluster Complexes Bearing Three Quadruply Bridging CO Ligands: X-ray Crystal Structure of [C₅H₃(SiMe₃)₂]WRu₆(μ₃-H)- (CO)₁₈

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Generation of Oxo−Carbide Clusters from Direct Scission of a Coordinated Carbonyl Ligand: Molecular Structures of Cp2W2Ru3(CO)13 and Cp*W(O)Cp*WRu3(μ5-C)(CO)11

Cited by 28 publications

References 41 publications

Alkyne−Acetylide Coupling in Cluster Compounds Bearing a Triosmium Carbonyl Os3(CO)8 Fragment and a High Oxidation State (C5Me5)W(O)2 Unit

Alkyne−Acetylide Coupling in Cluster Compounds Bearing a Triosmium Carbonyl Os3(CO)8 Fragment and a High Oxidation State (C5Me5)W(O)2 Unit

Competitive Acetylide C−C Bond Scission vs Formation of a Quadruply Bridging Carbonyl Ligand. X-ray Crystal Structures of the Two Pentanuclear Clusters Cp*3W3Ru2(μ4-C)(μ3-CPh)(CO)9 and Cp*3W3Ru2(μ3-CCBut)(CO)9

Synthesis of the First Cluster Complexes Bearing Three Quadruply Bridging CO Ligands: X-ray Crystal Structure of [C5H3(SiMe3)2]WRu6(μ3-H)- (CO)18

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Generation of Oxo−Carbide Clusters from Direct Scission of a Coordinated Carbonyl Ligand: Molecular Structures of Cp₂W₂Ru₃(CO)₁₃ and CpW(O)CpWRu₃(μ₅-C)(CO)₁₁

Alkyne−Acetylide Coupling in Cluster Compounds Bearing a Triosmium Carbonyl Os₃(CO)₈ Fragment and a High Oxidation State (C₅Me₅)W(O)₂ Unit

Alkyne−Acetylide Coupling in Cluster Compounds Bearing a Triosmium Carbonyl Os₃(CO)₈ Fragment and a High Oxidation State (C₅Me₅)W(O)₂ Unit

Competitive Acetylide C−C Bond Scission vs Formation of a Quadruply Bridging Carbonyl Ligand. X-ray Crystal Structures of the Two Pentanuclear Clusters Cp₃W₃Ru₂(μ₄-C)(μ₃-CPh)(CO)₉ and Cp₃W₃Ru₂(μ₃-CCBu^t)(CO)₉

Synthesis of the First Cluster Complexes Bearing Three Quadruply Bridging CO Ligands: X-ray Crystal Structure of [C₅H₃(SiMe₃)₂]WRu₆(μ₃-H)- (CO)₁₈