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

Koridze, A. A.; Zdanovich, V. I.; Шелоумов, А. М.; Lagunova, V. Yu.; Petrovskii, P. V.; Peregudov, A. S.; Dolgushin, and Fedor M.; Yanovsky, A. I.

doi:10.1021/om961017m

Cited by 24 publications

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“…On the contrary, the phenomenon of co-crystallization of neutral organometallic compounds is documented to a much lesser extent. To date, only a few co-crystals of metalcontaining complexes, for example, of mono-and bis(arene) derivatives of the hexaruthenium cluster, 20 trinuclear and tetranuclear ruthenium clusters, 21 copper complexes with different oxidation states, 22 and multicomponent nickelcontaining compounds, 23 have been reported.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Kinetic and Thermodynamic Pathways in the Reactions of Five-Membered Zircona- and Hafnacyclocumulenes with Acetonitrile. Structures and Mechanisms of Formation of the Obtained Complexes

et al. 2023

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The heating of five-membered zircona- and hafnacyclocumulene complexes (7) with a 2-fold excess of acetonitrile results in the formation of dimeric metallaazacyclopentadiene complexes (6), bicyclic amidine complexes (5), and tricyclic metallacycles (2). These three classes of compounds can be considered as kinetically (6) and thermodynamically (2 and 5) favorable products, the yield of which depends on both the process conditions and the structure of the initial complexes. On the basis of experimental and theoretical data, for all three types of products the reaction proceeds through the formation of monomeric metallaazacyclopentadienes (4) that are competitive.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Kinetic and Thermodynamic Pathways in the Reactions of Five-Membered Zircona- and Hafnacyclocumulenes with Acetonitrile. Structures and Mechanisms of Formation of the Obtained Complexes

et al. 2023

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“…However, the corresponding SiMe 3 1 or SnMe 3 derivatives are stable [1]. While these properties have limited the application of this diyne as a ligand, the literature contains accounts of complexes derived from Co 2 (CO) 8 [1], Ru 3 (CO) 12 [2], Os 3 (CO) 12 [3], PtCl 2 Ph(PR 3 ) 2 and related oligomeric materials [4]. The rutheniumevinylidene complex {Fc'[C (SiMe 3 )¼C¼]} 2 RuCl 2 (PPr i 3 ) 2 is also known [5].…”

Section: Introductionmentioning

confidence: 99%

Phosphine-gold(I) derivatives of 1,1′-bis(alkynyl)metallocenes: Molecular structures of Fc’(CCX)2 [X = Au(PPh3), SiMe3] and Au4{(CC)2Fc’}2(PPh3)2 [Fc’ = Fe(η-C5H4-)2]

Bruce

Jevric

Skelton

et al. 2010

Journal of Organometallic Chemistry

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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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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

Cited by 24 publications

References 36 publications

Kinetic and Thermodynamic Pathways in the Reactions of Five-Membered Zircona- and Hafnacyclocumulenes with Acetonitrile. Structures and Mechanisms of Formation of the Obtained Complexes

Kinetic and Thermodynamic Pathways in the Reactions of Five-Membered Zircona- and Hafnacyclocumulenes with Acetonitrile. Structures and Mechanisms of Formation of the Obtained Complexes

Phosphine-gold(I) derivatives of 1,1′-bis(alkynyl)metallocenes: Molecular structures of Fc’(CCX)2 [X = Au(PPh3), SiMe3] and Au4{(CC)2Fc’}2(PPh3)2 [Fc’ = Fe(η-C5H4-)2]

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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