Conversion of the cluster [Os3(CHCFc)(CO)10] (CHCFc = ethynylferrocene) into [Os3(S)(CHCFc)(CO)9] by reaction with sulphur. Crystal structures of these clusters and of [Os3H(C2Fc)(CO)9]

Hardcastle, Kenneth I.; Deeming, Antony J.; Nuel, Didier; Powell, Nicholas I.

doi:10.1016/0022-328x(89)85116-2

Cited by 26 publications

(8 citation statements)

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“…The structure of molecule 1a as determined in the crystal of II is shown in Figure . Complexes of this type, including the osmium analog of 1a , Os 3 H(C⋮CFc)(CO) 9 ( 6 ), have been studied earlier by diffraction methods . The Ru(5)-Ru(7) bond in 1a is somewhat longer than the two other bonds in the metal triangle.…”

Section: Resultsmentioning

confidence: 99%

“…IR spectra were recorded on a Bruker IFS-113v spectrometer and 1 H and 13 C NMR spectra on a Bruker AMX-400 instrument. The Ru 3 H(C⋮CFc)(CO) 9 and Os 3 H(C⋮CFc)(CO) 9 complexes were prepared according to published procedures. 8a, The 13 CO-enriched samples ( ca . 40% 13 C) of compounds 2a and 2b were prepared by reaction of Ru 3 ( 13 CO) 12 with 1a and 1b , respectively.…”

Section: Methodsmentioning

confidence: 99%

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Synthesis of the Tetranuclear Clusters RuM₃H(C⋮CFc)(CO)₁₂ (M = Ru, Os; Fc = Ferrocenyl), Containing a Fluxional μ₄-Acetylide Ligand. Structure of a Mixed Crystal Containing Tetranuclear (Ru₄H(C⋮CFc)(CO)₁₂) and Trinuclear (Ru₃H(C⋮CFc)(CO)₉) Ruthenium Complexes

et al. 1997

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Reactions of acetylide clusters M3H(C⋮CFc)(CO)9 (1a, M = Ru; 1b, M = Os; Fc = ferrocenyl) with Ru3(CO)12 in refluxing hexane yield the tetranuclear clusters RuM3H(C⋮CFc)(CO)12 (2a,b) with a butterfly metal core. The μ4-acetylide ligand of these complexes undergoes migration, indicated by variable-temperature 1H and 13C NMR studies. Compounds 2a and 2b are relatively unstable in solution as well as in the solid state and decompose with formation of corresponding trinuclear acetylide precursors and Ru3(CO)12. The molecular structures of 1a and 2a were established by the X-ray diffraction study of a mixed crystal, which contains both clusters in a 1:1 ratio.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Synthesis of the Tetranuclear Clusters RuM₃H(C⋮CFc)(CO)₁₂ (M = Ru, Os; Fc = Ferrocenyl), Containing a Fluxional μ₄-Acetylide Ligand. Structure of a Mixed Crystal Containing Tetranuclear (Ru₄H(C⋮CFc)(CO)₁₂) and Trinuclear (Ru₃H(C⋮CFc)(CO)₉) Ruthenium Complexes

et al. 1997

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“…There are 26 compounds containing an FeOs 3 cluster [288,[291][292][293][294][295][296][297][298][299][300][301][302][303][304][305][306][307], Their crystallographic and structural parameters are given in Table 5.…”

Section: <= _mentioning

confidence: 99%

“…28, Nos. 4-5-6, 2008 Crystallographic and Structural Analysis Of Iron Heterometallic Compounds cyclopentadienylphosphido-P,f,/')-nonacarbonyl-iron-tri-osmium [297] All remaining FeOs3 clusters [294][295][296][298][299][300][301][302][303][304][305][306][307] contain an Os3C framework with a ferrocene or a substituted ferrocene moiety bonded to a μ3bridging alkylidene carbon atom. The Os-Os distances range from 2.7476 (9) to 3.1038(6) A.…”

Section: <= _mentioning

confidence: 99%

“…Only four FeM 3 clusters contain a non-transition metal, namely Sn [245], Bi [246] and Te [247,248]. All remaining clusters contain the following transition metals with the number of specimen in parenthesis: Ag [249], Zn [252], Ta [253], W [66], Rh [290], Ir [236] (each xl); Au [250,251], Cr [254,254], Ni [273,274] (each x2); Mo (x4) [177,256,257]; Co (xl8) [258][259][260][261][262][263][264][265][266][267][268][269][270][271][272]; Os (x26) [288,[291][292][293][294][295][296][297][298][299][300][301][302]…”

Section: <= _mentioning

confidence: 99%

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Sundberg¹,

Holloway²

2008

Reviews in Inorganic Chemistry

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In total, 430 heterotetranuclear iron clusters have been included in this review, containing the Fe 3 M, Fe 2 M 2 , Fe 2 MM', FeM 2 M' and FeMM'M" cores. About 25 % of the clusters contain non-transition metals (17 different elements). The shortest bond is the Fe-Ge bond of 2.321(10) A. The remaining examples (about 75 %) contain transition metals (21 different elements) in clusters with iron displaying a rich and complex chemistry. The shortest bond in this category is the Fe-Ni bond of 2.277(11) Ä. Correlations between structural parameters containing heteronuclear and ligand donor atoms are given. Furthermore, an overall summary of the metal-metal distances is given and the observed trends are discussed.

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Redox behavior of trinuclear M3(μ-H)(μ3-μ1:μ2:μ2-C2Fe)(Co)9 and tetranuclear RuM3 3(μ-H)(μ4-μ1:μ1:μ1:μ2-C2Fe)(Co)12 (M=Ru or Os; and Fc=ferrocenyl) clusters. Electronic interaction between the ferrocenylacetylide ligand and the metal core of the cluster

et al. 1997

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The redox properties of the clusters Ru.-.,(CO)I? (1), Ru3(lx-H)(g3-rll:q2:rl2-C2Fc)(CO)9 (2), Os3(g-H)(t.t3-rll:~12:'q2-C2Fc)(CO)9 (3), Ru,~(la-H)(tx4-rli:atl:rli:rl2-C2Fc)(CO)t2 (4), and RuOs3(p,-H)(g4-~11:rll:rl~:rl2-C2Fc)(CO)12 (5) in THF have been studied by cyclic voltammetry in the lemperature range from -60 to +20 ~ It was demonstrated that reversible oneelectron oxidation of the ferrocenyl fragment in clusters 2--5 occurs at more positive potentials (As ~ = 0.15--0.26 V) than that of free ferrocene. This is indicative of the electron-withdrawing character of the cluster core with respect to the ferrocenylacetylide iigand. The electron-withdrawing effect of the metal core is more pronounced in tetranuclear clusters 4 and 5 than in trinuclear clusters 2 and 3. Unlike complexes I--3, which undergo irreversible reduction, complexes 4 and 5 undergo reversible one-electron reduction to form the corresponding radical anions 4"-and 5"-Key words: ruthenium clusters, o~mium clusters, osmium--ruthenium mixed clusters: ferrecenylacetytide ligand; cyclic voltammetw.It is known that polydentate coordination of hydrocarbon moieties to several metal centers of transitionmetal clusters has a pronounced effect on their reactivities. t Thus, under mild conditions, hydrocarbon ligands in acetylene and ethylene derivatives of the carbonyl clusters of metals add not only N-and P-nucleophiles 2,3 but uncharged C-nucleophiles as well. 4,5 It is evident that studies of the mutual electronic effect of the hydrocarbon ligands and the metal core in the clusters is of interest for an understanding of both the increased reactivities of these ligands and conversions of hydrocarbon substrates on the surface of heterogeneous catalysts. It is also known that because ferrocene cart oxidize reversibly, the ferrocene-ferricenium system is a very. sensitive indicator for studying the electronic properties of the substituents in the cycIopentadienyl ring as well as for estimating the degree of electronic interactions of different redox centers, which are present in a single molecule. 6,7 Therefore, studies of the redox properties of ferrocene-containing clusters is of obvious interest. In principle, the electronic interaction between two centers of one molecule should be accompanied by a change in the redox properties of these centers. 7 These data are most convenient to obtain by cyclic voltammetry.Therefore, in this work we studied the redox behavior of ruthenium carbonyl Ru3(CO)I 2 (1), its ferrocenylacetylide derivative, namely, the trinuclear Ru3(~t-H)(i.t3-ql:@:rl2-C2Fc)(CO)9 cluster (2), 8,9 the triosmium analog Os3(I.t-H)(/.t3-rll:rl2:rl2-C2Fc)(CO)9 (3), 9A~ and the tetranuclear clusters with a "butterfly" core, Ru4(P.-H)(~4-rl t:rl t:.q t :q2_C2Fc)(CO ) 12 (4) l 1,1z and RuOs3(la_ H)(g4_rl t:r 1 l:r 1 t:q?_C2Fc)(CO) t2 (5). 11,1Z These compounds contain two redox-active centers, namely, the metal, core and the ferrocene unit, and are convenient models for studying the redistribution of the electron density upon coordination of acetyl...

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Conversion of the cluster [Os3(CHCFc)(CO)10] (CHCFc = ethynylferrocene) into [Os3(S)(CHCFc)(CO)9] by reaction with sulphur. Crystal structures of these clusters and of [Os3H(C2Fc)(CO)9]

Cited by 26 publications

References 16 publications

Synthesis of the Tetranuclear Clusters RuM₃H(C⋮CFc)(CO)₁₂ (M = Ru, Os; Fc = Ferrocenyl), Containing a Fluxional μ₄-Acetylide Ligand. Structure of a Mixed Crystal Containing Tetranuclear (Ru₄H(C⋮CFc)(CO)₁₂) and Trinuclear (Ru₃H(C⋮CFc)(CO)₉) Ruthenium Complexes

Synthesis of the Tetranuclear Clusters RuM₃H(C⋮CFc)(CO)₁₂ (M = Ru, Os; Fc = Ferrocenyl), Containing a Fluxional μ₄-Acetylide Ligand. Structure of a Mixed Crystal Containing Tetranuclear (Ru₄H(C⋮CFc)(CO)₁₂) and Trinuclear (Ru₃H(C⋮CFc)(CO)₉) Ruthenium Complexes

Contents

Redox behavior of trinuclear M3(μ-H)(μ3-μ1:μ2:μ2-C2Fe)(Co)9 and tetranuclear RuM3 3(μ-H)(μ4-μ1:μ1:μ1:μ2-C2Fe)(Co)12 (M=Ru or Os; and Fc=ferrocenyl) clusters. Electronic interaction between the ferrocenylacetylide ligand and the metal core of the cluster

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Conversion of the cluster [Os3(CHCFc)(CO)10] (CHCFc = ethynylferrocene) into [Os3(S)(CHCFc)(CO)9] by reaction with sulphur. Crystal structures of these clusters and of [Os3H(C2Fc)(CO)9]

Cited by 26 publications

References 16 publications

Synthesis of the Tetranuclear Clusters RuM3H(C⋮CFc)(CO)12 (M = Ru, Os; Fc = Ferrocenyl), Containing a Fluxional μ4-Acetylide Ligand. Structure of a Mixed Crystal Containing Tetranuclear (Ru4H(C⋮CFc)(CO)12) and Trinuclear (Ru3H(C⋮CFc)(CO)9) Ruthenium Complexes

Synthesis of the Tetranuclear Clusters RuM3H(C⋮CFc)(CO)12 (M = Ru, Os; Fc = Ferrocenyl), Containing a Fluxional μ4-Acetylide Ligand. Structure of a Mixed Crystal Containing Tetranuclear (Ru4H(C⋮CFc)(CO)12) and Trinuclear (Ru3H(C⋮CFc)(CO)9) Ruthenium Complexes

Contents

Redox behavior of trinuclear M3(μ-H)(μ3-μ1:μ2:μ2-C2Fe)(Co)9 and tetranuclear RuM3 3(μ-H)(μ4-μ1:μ1:μ1:μ2-C2Fe)(Co)12 (M=Ru or Os; and Fc=ferrocenyl) clusters. Electronic interaction between the ferrocenylacetylide ligand and the metal core of the cluster

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Synthesis of the Tetranuclear Clusters RuM₃H(C⋮CFc)(CO)₁₂ (M = Ru, Os; Fc = Ferrocenyl), Containing a Fluxional μ₄-Acetylide Ligand. Structure of a Mixed Crystal Containing Tetranuclear (Ru₄H(C⋮CFc)(CO)₁₂) and Trinuclear (Ru₃H(C⋮CFc)(CO)₉) Ruthenium Complexes

Synthesis of the Tetranuclear Clusters RuM₃H(C⋮CFc)(CO)₁₂ (M = Ru, Os; Fc = Ferrocenyl), Containing a Fluxional μ₄-Acetylide Ligand. Structure of a Mixed Crystal Containing Tetranuclear (Ru₄H(C⋮CFc)(CO)₁₂) and Trinuclear (Ru₃H(C⋮CFc)(CO)₉) Ruthenium Complexes