Decacarbonyl‐(η
 5
 ‐Cyclopentadienyl)Dihydridocobalttriosmium, CoOs
 3
 (μ‐H)
 2
 (η
 5
 ‐C
 5
 H
 5
 )(μ‐CO)(CO)
 9
 ; Nonacarbonyl‐(η
 5
 Cyclopentadienyl)Trihydrido‐ and (η
 5
 ‐Cyclopentadienyl)Tetrahydridocob

Jan, Deng-Yang; Coffy, Tim J.; Hsu, Wen‐Liang; Shore, Sheldon G.; Handwerker, Beth M.; Geoffroy, Gregory L.

doi:10.1002/9780470132562.ch47

Cited by 2 publications

(1 citation statement)

References 12 publications

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“…Extensive studies have also been carried out with the isoelectronic dirhenium complex [Re 2 (μ-H) 2 (CO) 8 ], which reacts easily with different transition-metal complexes such as the metal carbonyl anions [M(CO) x ] - (M = Mn, Re, Ir; x = 4, 5) and [Re 2 H(CO) 9 ] - 8a,9 or the neutral late transition-metal compounds [Pt(PPh 3 ) 2 (C 2 H 4 )], [Pt(COD) 2 ], or [Ir(CO)(η 5 -C 9 H 7 )(η 2 -C 8 H 14 )], to give new tri- or tetranuclear clusters. Finally, the reactivity of the triosmium dihydride [Os 3 (μ-H) 2 (CO) 10 ] toward organometallic fragments has been also widely studied, allowing the synthesis of heterometallic clusters with higher nuclearity and incorporating transition-metal atoms from groups 6, , 8, − 9, − 10, 19a, 11, 19a, and 12 …”

Section: Introductionmentioning

confidence: 99%

Reactivity of the Unsaturated Hydride [Mo₂(η⁵-C₅H₅)₂(μ-H)(μ-PCy₂)(CO)₂] toward 17- and 16-Electron Metal Carbonyl Fragments: Rational Synthesis of Electron-Deficient Heterometallic Clusters

et al. 2006

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Reactions of the 30-electron hydride [Mo2Cp2(μ-H)(μ-PCy2)(CO)2] (Cp = η5-C5H5) with the 17-electron-fragment precursors [M2Cp2(CO) n ] (M = Mo, W, n = 6; M = Ru, n = 4) or [Mn2(CO)10] lead to the 46-electron clusters [Mo2MCp3(μ-PCy2)(μ3-CO)(CO)4] (M = Mo, W), [Mo2RuCp3(μ-PCy2)(μ-CO)(CO)3], and [MnMo2Cp2(μ-PCy2)(μ-CO)2(CO)5]. The structure of the trimolybdenum cluster was confirmed by an X-ray diffraction study and displays two long (ca. 3.1 Å) and one short Mo−Mo distance (2.743(1) Å). The title unsaturated hydride also proved to be highly reactive toward the appropriate precursors of 16-electron fragments such as M(CO)5 (M = Cr, Mo, W) and MnCp‘(CO)2 (Cp‘ = η5-C5H4CH3), then leading to the 46-electron hydride clusters [MMo2Cp2(μ3-H)(μ-PCy2)(CO)7] (M = Cr, Mo, W) and [MnMo2Cp2Cp‘(μ3-H)(μ-PCy2)(CO)4]. The structures of the compounds having Mo2W and Mo2Mn skeletons were also determined by X-ray diffraction methods, both of them displaying Mo−Mo distances (ca. 2.6 Å) somewhat shorter than expected for double MoMo bonds and Mo−M distances longer than the corresponding single-bond lengths. A similar reaction takes place with the 12-electron compound CuCl, to give the hydride [CuMo2ClCp2(μ3-H)(μ-PCy2)(CO)2]. In contrast, the reaction of the title hydride with [Fe2(CO)9], a precursor of the 16-electron fragment Fe(CO)4, gives the heterodinuclear complex [FeMo(μ-PCy2)(CO)6] (Fe−Mo = 2.931(1) Å).

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Section: Introductionmentioning

confidence: 99%

Reactivity of the Unsaturated Hydride [Mo₂(η⁵-C₅H₅)₂(μ-H)(μ-PCy₂)(CO)₂] toward 17- and 16-Electron Metal Carbonyl Fragments: Rational Synthesis of Electron-Deficient Heterometallic Clusters

et al. 2006

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Heterometallic Derivatives of the Unsaturated Ditungsten Hydride [W₂(η⁵-C₅H₅)₂(H)(μ-PCy₂)(CO)₂]

et al. 2013

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The title complex reacted with different transition-metal (M) complexes to give heterometallic clusters with W2M and W2M2 metal cores. The reaction with [Fe2(CO)9] in THF at room temperature gave a mixture of the heterodinuclear compound [FeWCp(μ-PCy2)(CO)6] and the tetrahedral clusters [Fe2W2Cp2(μ3-H)(μ-PCy2)(CO)8] (W-W = 2.704(1) Å) and [Fe2W2Cp2(μ-H)(μ-PCy2)(μ-CO)(CO)8] (W-W = 3.058(5) Å). In contrast, its reaction with [Ru3(CO)12] under ultraviolet-visible (UV-Vis) irradiation gave only the heterodinuclear complex [RuWCp(μ-PCy2)(CO)6]. The title complex also reacted readily with [M(CO)6] (M = Cr, Mo, W) in toluene solution under UV-Vis irradiation, but the main product was the known tetracarbonyl complex [W2Cp2(μ-H)(μ-PCy2)(CO)4], except in the reaction with [W(CO)6], the latter also yielding the expected 46-electron cluster [W3Cp2(μ3-H)(μ-PCy2)(CO)7] in 40% yield. The title complex reacted under visible-UV irradiation with different metal-metal bonded dimers in toluene solution, but only with [Ru2Cp2(CO)4] an heterometallic cluster was obtained, with composition [RuW2Cp3(μ-PCy2)(CO)4]. Its reaction with the tetrahydroborate complex [Cu(BH4)(PPh3)2] led to the insertion of two CuH(PPh3) fragments and release of BH3·PPh3, to give the tetranuclear cluster [Cu2W2Cp2(μ-H)3(μ-PCy2)(CO)2(PPh3)2], which exists in solution as an equilibrium mixture of two isomers.

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Decacarbonyl‐(η ⁵ ‐Cyclopentadienyl)Dihydridocobalttriosmium, CoOs ₃ (μ‐H) ₂ (η ⁵ ‐C ₅ H ₅ )(μ‐CO)(CO) ₉ ; Nonacarbonyl‐(η ⁵ Cyclopentadienyl)Trihydrido‐ and (η ⁵ ‐Cyclopentadienyl)Tetrahydridocob

Cited by 2 publications

References 12 publications

Reactivity of the Unsaturated Hydride [Mo₂(η⁵-C₅H₅)₂(μ-H)(μ-PCy₂)(CO)₂] toward 17- and 16-Electron Metal Carbonyl Fragments: Rational Synthesis of Electron-Deficient Heterometallic Clusters

Reactivity of the Unsaturated Hydride [Mo₂(η⁵-C₅H₅)₂(μ-H)(μ-PCy₂)(CO)₂] toward 17- and 16-Electron Metal Carbonyl Fragments: Rational Synthesis of Electron-Deficient Heterometallic Clusters

Heterometallic Derivatives of the Unsaturated Ditungsten Hydride [W₂(η⁵-C₅H₅)₂(H)(μ-PCy₂)(CO)₂]

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Decacarbonyl‐(η 5 ‐Cyclopentadienyl)Dihydridocobalttriosmium, CoOs 3 (μ‐H) 2 (η 5 ‐C 5 H 5 )(μ‐CO)(CO) 9 ; Nonacarbonyl‐(η 5 Cyclopentadienyl)Trihydrido‐ and (η 5 ‐Cyclopentadienyl)Tetrahydridocob

Cited by 2 publications

References 12 publications

Reactivity of the Unsaturated Hydride [Mo2(η5-C5H5)2(μ-H)(μ-PCy2)(CO)2] toward 17- and 16-Electron Metal Carbonyl Fragments: Rational Synthesis of Electron-Deficient Heterometallic Clusters

Reactivity of the Unsaturated Hydride [Mo2(η5-C5H5)2(μ-H)(μ-PCy2)(CO)2] toward 17- and 16-Electron Metal Carbonyl Fragments: Rational Synthesis of Electron-Deficient Heterometallic Clusters

Heterometallic Derivatives of the Unsaturated Ditungsten Hydride [W2(η5-C5H5)2(H)(μ-PCy2)(CO)2]

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Decacarbonyl‐(η ⁵ ‐Cyclopentadienyl)Dihydridocobalttriosmium, CoOs ₃ (μ‐H) ₂ (η ⁵ ‐C ₅ H ₅ )(μ‐CO)(CO) ₉ ; Nonacarbonyl‐(η ⁵ Cyclopentadienyl)Trihydrido‐ and (η ⁵ ‐Cyclopentadienyl)Tetrahydridocob

Reactivity of the Unsaturated Hydride [Mo₂(η⁵-C₅H₅)₂(μ-H)(μ-PCy₂)(CO)₂] toward 17- and 16-Electron Metal Carbonyl Fragments: Rational Synthesis of Electron-Deficient Heterometallic Clusters

Reactivity of the Unsaturated Hydride [Mo₂(η⁵-C₅H₅)₂(μ-H)(μ-PCy₂)(CO)₂] toward 17- and 16-Electron Metal Carbonyl Fragments: Rational Synthesis of Electron-Deficient Heterometallic Clusters

Heterometallic Derivatives of the Unsaturated Ditungsten Hydride [W₂(η⁵-C₅H₅)₂(H)(μ-PCy₂)(CO)₂]