Novel coordination modes of partially hydrogenated diyne ligands on metal carbonyl clusters †

Clarke, Lionel P.; Davies, John E.; Raithby, P. R.; Shields, Gregory P.

doi:10.1039/b006810l

Cited by 17 publications

(13 citation statements)

References 24 publications

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“…The unprecedented activation of five C(sp 3 )-H bonds of linear alkenes has been observed on studying reactions of compound 12 with linear 1-alkenes, which give cluster products that contain trienyl ligands (45)(46)(47).…”

Section: Discussionmentioning

confidence: 99%

“…That paper reports the synthesis of [Ru 4 (µ 4 -RCH 2 C 3 R)(CO) 12 ] (R ) Me, SiMe 3 , Ph) by reactions of [Ru 4 (µ-H) 4 (CO) 12 ] with the corresponding diynes. 47 It is also interesting to note that metal complexes of conjugated transenynes are unprecedented.…”

Section: Reactivity Of [Ru 6 (µ 3 -H) 2 (µ 5 -K 2 -Ampy)(µ-co) 2 (Co)...mentioning

confidence: 99%

“…As far as we are aware, there is only one additional report describing the 1,1-hydrogenation of a diyne CC bond. That paper reports the synthesis of [Ru 4 (μ 4 -RCH 2 C 3 R)(CO) 12 ] (R = Me, SiMe 3 , Ph) by reactions of [Ru 4 (μ-H) 4 (CO) 12 ] with the corresponding diynes . It is also interesting to note that metal complexes of conjugated trans -enynes are unprecedented.…”

Section: Reactivity Of [Ru6(μ3-h)2(μ5-κ2-ampy)(μ-co)2(co)14] (12)mentioning

confidence: 99%

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Basal-Edge-Bridged Square-Pyramidal Hexaruthenium Carbonyl Clusters: Synthesis, Structure, and Reactivity

Cabeza

García‐Álvarez

2008

Organometallics

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This paper reviews the current knowledge on the synthesis, structure, and reactivity of basal-edgebridged square-pyramidal hexaruthenium carbonyl cluster complexes, covering the literature up to the end of 2007. These clusters are generally prepared at high temperature (>100 °C) through processes that involve a ligand-promoted condensation of two triruthenium clusters. All cluster complexes of this type contain a bridging ligand with an S-, C-, or N-donor fragment capping the four basal metal atoms of the pyramid. When the bridging ligand is bi-or polydentate, it is also bound to the edge-bridging metal atom. The reactivity of [Ru 6 (µ 3 -H) 2 (µ 5 -κ 2 -ampy)(µ-CO) 2 (CO) 14 ] (H 2 ampy ) 2-amino-6-methylpyridine) with various reagents has been recently investigated. Its reactions with unsaturated hydrocarbons (carbocycles, alkynes, diynes, alkenes) often involve multisite coordination and hydrogenation or dehydrogenation of the original reagents. The release of an Ru(CO) n fragment (the only one that is not bound to the bridging ampy ligand) or its exchange between hexanuclear species is also frequently observed. This leads to penta-and heptanuclear clusters as final products. The reactivity of [Ru 6 (µ 3 -H) 2 (µ 5 -κ 2 -ampy)(µ-CO) 2 (CO) 14 ] with other reagents (triphenylphosphine, hydrides, H 2 ampy) and its thermolysis in solution are also surveyed.

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Section: Discussionmentioning

confidence: 99%

Section: Reactivity Of [Ru 6 (µ 3 -H) 2 (µ 5 -K 2 -Ampy)(µ-co) 2 (Co)...mentioning

confidence: 99%

Section: Reactivity Of [Ru6(μ3-h)2(μ5-κ2-ampy)(μ-co)2(co)14] (12)mentioning

confidence: 99%

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Basal-Edge-Bridged Square-Pyramidal Hexaruthenium Carbonyl Clusters: Synthesis, Structure, and Reactivity

Cabeza

García‐Álvarez

2008

Organometallics

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“…These studies have shown that the cluster chemistry of diynes is very rich and that it strongly depends on the nature of the metal cluster and the diyne used. [1][2][3][4][5][6][7][8][9][10] Most metal clusters whose reactivity with diynes has been studied contain no hydride ligands. These clusters react with diynes to give products in which the diynes behave as alkyne ligands.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of Diphenylbutadiyne with a Hexaruthenium Dihydride. Unusual 1,1- and trans-1,2-Additions of Two Hydrogen Atoms to an Internal CC Triple Bond

et al. 2006

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The reactions of the basal edge-bridged square pyramidal hexanuclear cluster [Ru6(μ3-H)2(μ5-κ2-ampy)(μ-CO)2(CO)14] (1; H2ampy = 2-amino-6-methylpyridine) with diphenylbutadiyne give mixtures of cluster compounds, the composition of which depends on the reaction time and temperature. The following products have been isolated and characterized: [Ru6(μ5-κ2-ampy)(μ5-η3-PhCCCCH2Ph)(μ-CO)(CO)14] (two isomers, 2 and 3), [Ru6(μ5-κ2-ampy)(μ5-η4-trans-PhCCCHCHPh)(μ-CO)(CO)14] (4), and [Ru5(μ5-κ2-ampy)(μ4-η2-trans-PhCCCHCHPh)(η6-PhMe)(μ-CO)(CO)9] (5). In all products, the ampy ligand is attached to five metal atoms through its nitrogen atoms, in the same way as in complex 1. These compounds represent unusual examples of 1,1- and trans-1,2-additions of two hydrogen atoms to an internal CC triple bond, since 2 and 3 contain a hydrocarbon ligand that arises from the migration of the original hydrides of 1 onto a terminal carbon atom of the diyne C4 chain, and 4 and 5 contain a 1,4-diphenyl-trans-butenyne ligand. The reaction pathway 1 + PhC2C2Ph → 2 → 3 → 4 → 5 has been established by studying the individual thermolysis of compounds 2−4 and reactions of 1 with diphenylbutadiyne at different reaction times and temperatures.

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“…The cluster consists of a tetranuclear cluster in butterfly geometry with an allene type ligand which donates six electrons to the cluster. A similar structure has been described by Raithby et al 16 but that one was obtained from the reaction of [μ 4 -H 4 Ru 4 (CO) 12 ] with diynes. Bond parameters are very similar to those reported previously and compound 2 also has two semi-bridging carbonyl groups.…”

Section: Resultsmentioning

confidence: 69%

Coupling of acetylene molecules on ruthenium clusters, involving cleavage of C–Si bonds in the alkyne and coordination of a phenyl ring of a SiPh3 group

2013

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The reaction of [Ru3(CO)12] with the disubstituted acetylene Me3SiC≡CSiMe3 yields several compounds where cleavage of the C-Si bond has occurred thus allowing an easy coupling of carbon fragments to produce allene complexes [Ru4(CO)12(μ4-η(3)-Me3SiCCCSiMe3)] (2), differently substituted metallacycle compounds [Ru3(μ2-CO)2(CO)6{μ3-C(R)C(SiMe3)C(R')C(SiMe3)}] (3) [R = SiMe3, R' = CH3 (3a); R = H, R' = CH3 (3b); R = C≡CSiMe3; R' = H (3c)] and a pentanuclear ruthenium cluster containing three separate alkyne units; two with one SiMe3 substituent and one with two SiMe3 substituents, coordinated to the metal framework [Ru5(CO)12{μ3-(C2SiMe3)2}μ2-C2(SiMe3)2] (4). Another product of the reaction is the acetylide derivative [(μ-H)Ru3(CO)9(CCSiMe3)] (1a). In order to determine if this was an intermediate for the formation of the products already mentioned, the reaction of this compound was carried out with the two terminal alkynes HCCSiMe3 and HCCSiPh3. In the case of the reaction with the SiMe3 derivative, products included the same metallocyclopentadiene derivatives as well as the pentanuclear cluster already mentioned. If the acetylene is the SiPh3 derivative, products show coupling of SiPh3CC units with CCSiMe3 fragments and CO molecules, coordinated to mononuclear [Ru(CO)2(CCSiPh3){η(5)-(CCSiPh3)2C(OH)}] (7), dinuclear [Ru2(CO)3{Ph3Si(H)CC(H)CC(SiMe3)C(O)C(SiPh3)C(H)}] (8) and trinuclear [Ru3(CO)4{(Ph3Si(H)CC(H)CC(SiMe3)}{(H)CC(SiPh3)C(O)}] (9) clusters. One important characteristic in compounds 8 and 9 is that one of the phenyl rings of the SiPh3 substituent is η(6) coordinated to a ruthenium atom. Compounds 2 to 4(a-c) and 7 to 9 were characterized spectroscopically and by X-ray diffraction.

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Novel coordination modes of partially hydrogenated diyne ligands on metal carbonyl clusters †

Cited by 17 publications

References 24 publications

Basal-Edge-Bridged Square-Pyramidal Hexaruthenium Carbonyl Clusters: Synthesis, Structure, and Reactivity

Basal-Edge-Bridged Square-Pyramidal Hexaruthenium Carbonyl Clusters: Synthesis, Structure, and Reactivity

Reactivity of Diphenylbutadiyne with a Hexaruthenium Dihydride. Unusual 1,1- and trans-1,2-Additions of Two Hydrogen Atoms to an Internal CC Triple Bond

Coupling of acetylene molecules on ruthenium clusters, involving cleavage of C–Si bonds in the alkyne and coordination of a phenyl ring of a SiPh3 group

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