Heterometallic carbonyl cluster oxide. Formation, structure and reactivity of WRe2 oxo-acetylide cluster compounds

Chi, Yun; Cheng, Puu-Shum; Wu, Hsiao-Ling; Hwang, Der-Kweng; Su, Pei-Chiun; Peng, Shie‐Ming; Lee, Gene‐Hsiang

doi:10.1039/c39940001839

Cited by 19 publications

(6 citation statements)

References 9 publications

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“…The W atom carries the η 5 -C 5 H 5 ring and the oxygen atom (W−O(1) = 1.716(5) Å) and forms a bridge to the cage atom B(5) through C(10) (W−C(10) = 2.082(6) Å, C(10)−B(5) = 1.62(1) Å). The W−O(1) separation may be compared with that in [W 2 O(μ-CC 6 H 4 Me-4)(CO) 2 (η 5 -7,8-Me 2 -7,8-C 2 B 9 H 9 )(η 5 -C 9 H 7 )] (C 9 H 7 = indenyl, 1.699(6) Å),14a [W 2 FeO{μ 3 -C 2 (C 6 H 4 Me-4) 2 }(CO) 5 (η 5 -C 5 H 5 ) 2 ] (1.726(7) Å),14b or [WRe 2 O{μ 3 -C⋮CC(Me)CH 2 }(CO) 8 (η 5 -C 5 Me 5 )] (1.699(6) Å) . Interestingly, the W−O(1) distance is very close to the mean value (1.711 Å) found for W−O bonds in many oxo−tungsten species where it has been demonstrated that such distances cannot be utilized to identify bond multiplicity .…”

Section: Resultsmentioning

confidence: 99%

Carborane Complexes of Ruthenium: Reactions of [Ru(THF)(CO)₂(η⁵-7,8-R₂-7,8-C₂B₉H₉)] (R = H or Me) with Alkylidyne Complexes of Molybdenum and Tungsten

et al. 1997

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The complex [Ru(THF)(CO)2(η5-7,8-C2B9H11)] (1a, THF = tetrahydrofuran) reacts with the alkylidyne reagents [M(⋮CC6H4Me-4)(CO)2(η5-C5H5)] (M = Mo or W) to give the compounds [MRu(μ-CC6H4Me-4)(CO)4(η5-7,8-C2B9H11)(η5-C5H5)] (M = W (2a), Mo (2b)), which readily isomerize to the species [MRu(CO)4{σ,η5-9-CH(C6H4Me-4)-7,8-C2B9H10}(η5-C5H5)] (M = W (3a), Mo (3b)). The structure of 3b was established by X-ray diffraction. The Mo(CO)2(η5-C5H5) fragment is attached to the closo-RuC2B9 framework by a Mo−Ru bond and a three-center two-electron B−H⇀Mo linkage involving a boron atom in an α site in the CCBBB ring ligating the ruthenium. The CH(C6H4Me-4) moiety bridges between the Ru(CO)2 group and the B atom located in the other α site in the CCBBB ring. The oxo complex [WRuO{μ-σ,η5-9-CH(C6H4Me-4)-7,8-C2B9H10}(CO)2(η5-C5H5)] (4a) is a side product in the formation of 3a, and it also was characterized by X-ray diffraction. Treatment of the species 3 with PMe3 affords the zwitterionic compounds [MRu(CO)4{η5-9-CH(PMe3)(C6H4Me-4)-7,8-C2B9H10}(η5-C5H5)] (M = W (5a), Mo (5b)). A single-crystal X-ray diffraction study of 5a revealed that the (OC)2W−Ru(CO)2 unit is bridged by the nido-9-CH(PMe3)(C6H4Me-4)-7,8-C2B9H10 group. The open C2B3 face is pentacoordinated to the Ru atom, and there is an exopolyhedral B−H⇀W bond involving a Bα atom in the CCBBB ring. The other Bα site carries the CH(PMe3)(C6H4Me-4) substituent. Reactions between the ruthenium reagent [Ru(THF)(CO)2(η5-7,8-Me2-7,8-C2B9H9)] (1b) and [W(⋮CC6H4Me-4)(CO)2(η5-C5H5)] gave [WRuO{μ-σ,η5-7,8-Me2-10-CH(C6H4Me-4)-7,8-C2B9H8}(CO)2(η5-C5H5)] (4b), [WRu(μ-H){μ-η5,η‘5-7,8-Me2-9-C5H4-10-CH2(C6H4Me-4)-7,8-C2B9H7}(CO)5] (6a), and [WRu{μ-σ,η5-2,7-Me2-8-CH2(C6H4Me-4)-9-C(H)O-2,7-C2B9H6}(CO)4(η5-C5H5)] (7a) that were separated by column chromatography. The corresponding reaction between 1b and [W(⋮CC6H4Me-2)(CO)2(η5-C5H5)] afforded [WRuO{μ-σ,η5-7,8-Me2-n-CH(C6H4Me-2)-7,8-C2B9H8}(CO)2(η5-C5H5)] (n = 9 (4c), 10 (4d)) and [WRu{μ-σ,η5-2,7-Me2-8-CH2(C6H4Me-2)-9-C(H)O-2,7-C2B9H6}(CO)4(η5-C5H5)] (7b). Treatment of 1b with [Mo(⋮CC6H4Me-n)(CO)2(η5-C5H5)] (n = 4 or 2) yielded [MoRu(μ-H){μ-η5,η‘5-7,8-Me2-9-C5H4-10-CH2(C6H4Me-n)-7,8-C2B9H7}(CO)5] (n = 4 (6b), 2 (6c)). The structures of 4b, 6b, and 7b were established by X-ray diffraction. In 6b, the (OC)3Mo(μ-H)Ru(CO)2 unit is bridged by a 7,8-Me2-9-C5H4-10-CH2(C6H4Me-4)-7,8-C2B9H7 moiety, a structure resulting from a linking of C5H5 and nido-C2B9 groups. The C5 ring is η5-coordinated to the molybdenum, while the open CCBBB face of the carborane cage is similarly attached to the ruthenium. In complex 7b, a nido-2,7-Me2-8-CH2(C6H4Me-2)-9-C(H)O-2,7-C2B9H6 cage system bridges the Ru−W bond with an η5-CB4 ring coordinated to the Ru atom and with the cage joined to the W atom by a B−W bond. In addition, the C(H)O group forms a second bridge linking the cage to the tungsten, with the latter coordinated by the formyl O atom.

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Section: Resultsmentioning

confidence: 99%

Carborane Complexes of Ruthenium: Reactions of [Ru(THF)(CO)₂(η⁵-7,8-R₂-7,8-C₂B₉H₉)] (R = H or Me) with Alkylidyne Complexes of Molybdenum and Tungsten

et al. 1997

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“…Earlier we reported the synthesis of the trinuclear oxo-acetylide complex (η 5 -C 5 Me 5 )W(O)Re 2 (CO) 8 (μ-CCPh) ( 1 ) and the products obtained from hydrogenation reactions …”

Section: Resultsmentioning

confidence: 99%

“…Mass spectra were obtained on a JEOL-HX110 instrument operating in the fast atom bombardment (FAB) mode. The metal acetylide complex (η 5 -C 5 Me 5 )W(O)Re 2 (CO) 8 (CCPh) was prepared according to literature procedures . All reactions were performed under nitrogen atmosphere using deoxygenated solvents dried with an appropriate reagent.…”

Section: Methodsmentioning

confidence: 99%

Oxo Ligand Reactivity and Bonding in the Dinuclear W−Re Oxo−Acetylide Complex (η⁵-C₅Me₅)W(O)Re(CO)₄(μ-H)(CCPh)

Chi

et al. 1996

Inorg. Chem.

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The trinuclear oxo−acetylide metal cluster (η5-C5Me5)W(O)Re2(CO)8(μ-CCPh) (1) reacts with thiophenol in refluxing toluene to afford the dinuclear metal complex (η5-C5Me5)W(O)Re(CO)4(μ-H)(μ-CCPh) (2) in 90% yield. Upon treatment with Me3NO in acetonitrile, complex 2 loses one CO ligand and is converted initially to an acetonitrile derivative, (η5-C5Me5)W(O)Re(CO)3(NCMe)(μ-H)(μ-CCPh) (4), and then to a head-to-tail dimer, [(η5-C5Me5)WRe(CO)3(μ-O)(μ-H)(μ-CCPh)]2 (5), through the formation of two W⋮O−Re bridges. Extended Hückel MO calculations indicate that the most likely site of electrophilic attack is the oxo oxygen atom, and in agreement with this prediction, protonation of 2 with CF3CO2H is suggested to give the unstable hydroxy complex 6.

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“…Our experience in the synthesis of these heterometallic clusters prompted us to investigate new heterometallic systems in which the transition-metal atoms are in the highly disparate oxidation states and coordination environment. Thus, we have synthesized a series of oxo−carbonyl cluster compounds, which contain an oxo or a dioxo metal fragment coordinated to the metal carbonyl unit, by direct oxidation of carbonyl precursor clusters or through cluster building reactions employing the dioxo acetylide complex Cp*W(O) 2 (CCPh) as one of the building blocks . It was anticipated that the incorporation of oxo ligands into these clusters would result in enhanced reactivity or other interesting changes to their molecular structures.…”

Section: Introductionmentioning

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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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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Heterometallic carbonyl cluster oxide. Formation, structure and reactivity of WRe2 oxo-acetylide cluster compounds

Cited by 19 publications

References 9 publications

Carborane Complexes of Ruthenium: Reactions of [Ru(THF)(CO)₂(η⁵-7,8-R₂-7,8-C₂B₉H₉)] (R = H or Me) with Alkylidyne Complexes of Molybdenum and Tungsten

Carborane Complexes of Ruthenium: Reactions of [Ru(THF)(CO)₂(η⁵-7,8-R₂-7,8-C₂B₉H₉)] (R = H or Me) with Alkylidyne Complexes of Molybdenum and Tungsten

Oxo Ligand Reactivity and Bonding in the Dinuclear W−Re Oxo−Acetylide Complex (η⁵-C₅Me₅)W(O)Re(CO)₄(μ-H)(CCPh)

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

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Heterometallic carbonyl cluster oxide. Formation, structure and reactivity of WRe2 oxo-acetylide cluster compounds

Cited by 19 publications

References 9 publications

Carborane Complexes of Ruthenium: Reactions of [Ru(THF)(CO)2(η5-7,8-R2-7,8-C2B9H9)] (R = H or Me) with Alkylidyne Complexes of Molybdenum and Tungsten

Carborane Complexes of Ruthenium: Reactions of [Ru(THF)(CO)2(η5-7,8-R2-7,8-C2B9H9)] (R = H or Me) with Alkylidyne Complexes of Molybdenum and Tungsten

Oxo Ligand Reactivity and Bonding in the Dinuclear W−Re Oxo−Acetylide Complex (η5-C5Me5)W(O)Re(CO)4(μ-H)(CCPh)

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

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Carborane Complexes of Ruthenium: Reactions of [Ru(THF)(CO)₂(η⁵-7,8-R₂-7,8-C₂B₉H₉)] (R = H or Me) with Alkylidyne Complexes of Molybdenum and Tungsten

Carborane Complexes of Ruthenium: Reactions of [Ru(THF)(CO)₂(η⁵-7,8-R₂-7,8-C₂B₉H₉)] (R = H or Me) with Alkylidyne Complexes of Molybdenum and Tungsten

Oxo Ligand Reactivity and Bonding in the Dinuclear W−Re Oxo−Acetylide Complex (η⁵-C₅Me₅)W(O)Re(CO)₄(μ-H)(CCPh)

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