New bridged ruthenium carboxylato complexes. Structure and catalytic activity

Rotem, Michal; Shvo, Youval; Goldberg, Israel; Shmueli, U.

doi:10.1021/om00089a029

Cited by 41 publications

(36 citation statements)

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“…The formation of (11) The complexes that we are now proposing are closely related to those previously isolated by Rotem et al [7], containing acetic acid units directly bound to the metal.…”

Section: Resultssupporting

confidence: 77%

“…The ruthenium carboxylato complexes (2) and (3) react with hydrogen at low temperature (50 and 100°C, respectively) to give the hydrido complexes RuH 2 (CO) 2 (PBu 3 ) 2 (5), Ru 4 H 4 -(CO) 9 (PBu 3 ) 3 (6) and (1) [Ru 6 (l-H) 6 (CO) 10 (l-PHBu)(l-PBu 2 ) 2 (PBu 3 ) 2 (l 6 -P)] (7), 6 (l-CO)(CO) 12 (l-PBu 2 )(PBu 3 ) 2 (l 6 -P)] (8), 8 (CO) 12 (l 3 -PBu)(l-PBu 2 )(PBu 3 ) 2 (l 6 -P)] (9), [Ru 3 -(l-H) 2 (CO) 7 (l 3 -PBu)(PBu 3 ) 2 ] (10) are formed [1d,1e] (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

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On the behaviour of Ru(I) and Ru(II) carbonyl acetates in the presence of H2 and/or acetic acid and their role in the catalytic hydrogenation of acetic acid

Salvini¹,

Frediani²,

Giannelli³

et al. 2005

Journal of Organometallic Chemistry

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The reactivity of phosphine substituted ruthenium carbonyl carboxylates Ru(CO) 2 (MeCOO) 2 (PBu 3 ) 2 , Ru 2 (CO) 4 (lMeCOO) 2 (PBu 3 ) 2 , Ru 4 (CO) 8 (l-MeCOO) 4 (PBu 3 ) 2 with H 2 and/or acetic acid was investigated by IR and NMR spectroscopy to clarify their role in the catalytic hydrogenation of acetic acid. Evidences were collected to suggest hydride ruthenium complexes as the catalytically active species. Equilibria among ruthenium hydrides and carboxylato complexes take place in the presence of hydrogen and acetic acid, that is in the conditions of the catalytic reaction. Nevertheless the presence of acetic acid reduces the rate of the formation of hydrides. Working at a very high temperature (180°C) polynuclear phosphido hydrides such as [Ru 6 (l-H) 6 (CO) 10 (l-PHBu)(l-PBu 2 ) 2 (PBu 3 ) 2 (l 6 -P)] were formed. These phosphido clusters are suggested as the resting state of the catalytic system.Furthermore the bi-or tetranuclear Ru(I) carboxylato complexes react with acetic acid giving a mononuclear ruthenium complex Ru(CO) 2 (MeCOO)(l-MeCOO)(PBu 3 ), containing a monodentate and a chelato acetato ligands. This complex was spectroscopically characterised. Its identity and structure were confirmed by its reactivity with stoichiometric amount of PPh 3 to give Ru(CO) 2 (Me-COO) 2 (PBu 3 )(PPh 3 ), a new mononuclear ruthenium carbonyl carboxylate containing two different phosphines, that was fully characterised.

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Section: Resultssupporting

confidence: 77%

Section: Introductionmentioning

confidence: 99%

On the behaviour of Ru(I) and Ru(II) carbonyl acetates in the presence of H2 and/or acetic acid and their role in the catalytic hydrogenation of acetic acid

Salvini¹,

Frediani²,

Giannelli³

et al. 2005

Journal of Organometallic Chemistry

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“…The final carboxylato complexes containing two terminal pyrazol ligands could be isolated and unambiguously characterized [19], the proposed intermediacy of pyrazolato complexes with terminal carboxylic acid ligands [28] is consistent with the observation of Shvo and co-workers, who isolated and crystallographically characterized the complex Ru 2 (CO) 4 (OOCPh) 2 (HOOCPh) 2 , in which two benzoic acid ligands are terminally coordinated via the oxo function, while the OH function forms an internal hydrogen bond to an oxygen atom of a benzoato bridge [10].…”

Section: Synthetic Methodssupporting

confidence: 78%

“…Thus, with formic, acetic or propionic acid, the reaction produces the polymers [Ru 2 (CO) 4 (OOCR) 2 ] n (R = H, Me, Et), which depoly- 2 ] n in quantitative yield; at 165 • C the reaction gives, in smaller yields, the dinuclear hexacarbonyl decomposition product Ru 2 (CO) 6 (OOCPh) 2 [8]. If the reaction with benzoic acid is carried out at 145 • C in toluene solution in a glass-lined autoclave, the main product is the isostructural complex Ru 2 (CO) 4 (OOCPh) 2 (HOOCPh) 2 , in which the two axial positions are occupied by benzoic acid molecules coordinated as two-electron ligands through the oxo function [10].…”

Section: Synthetic Methodsmentioning

confidence: 99%

“…The interrelationships of various diruthenium tetracarbonyl complexes formed upon reaction of Ru 3 (CO) 12 with various carboxylic acids RCOOH have been studied very carefully by Shvo and co-workers [29]. The complexes formed depend on the substituent R, the molar ratio of the reactants and on whether or not the reaction is carried out in an open or closed vessel; the results are summarized in Scheme 2.…”

Section: Carboxylato and Carboxamido Derivativesmentioning

confidence: 99%

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Sawhorse-type diruthenium tetracarbonyl complexes

Therrien

Süß‐Fink

2009

Coordination Chemistry Reviews

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Ruthenium‐Catalyzed Transvinylation – New Insights

et al. 2013

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The use of ruthenium complexes in transvinylation catalysis has been well established since the 1980s. However, the reaction mechanism and the active catalyst species, which is presumed to contain ruthenium carbonyl carboxylate entities, have so far remained elusive. In this work the synthesis and characterization of three novel ruthenium complexes comprising ruthenium carbonyl carboxylate structural motifs including two single crystal structures as well as the crystal structures of two known ruthenium complexes are reported. These new complexes and four known ruthenium complexes with appropriate structural motifs were applied in transvinylation catalysis. Mechanistic studies including identification and characterization of the active species, isotope labeling experiments and examination of the regio‐ and stereoselectivity of the transvinylation reaction are presented, resulting in the proposal of a probable reaction mechanism, which is supported by DFT calculations on the B3LYP/6‐31G* level of theory.magnified image

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New bridged ruthenium carboxylato complexes. Structure and catalytic activity

Cited by 41 publications

References 0 publications

On the behaviour of Ru(I) and Ru(II) carbonyl acetates in the presence of H2 and/or acetic acid and their role in the catalytic hydrogenation of acetic acid

On the behaviour of Ru(I) and Ru(II) carbonyl acetates in the presence of H2 and/or acetic acid and their role in the catalytic hydrogenation of acetic acid

Sawhorse-type diruthenium tetracarbonyl complexes

Ruthenium‐Catalyzed Transvinylation – New Insights

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