Homogeneous catalytic hydrogenation of free carboxylic acids in the presence of cluster ruthenium carbonyl hydrides

Bianchi, Mario; Menchi, Gloria; Francalanci, F.; Piacenti, Franco; Matteoli, Ugo; Frediani, Piero; Botteghi, C.

doi:10.1016/s0022-328x(00)83702-x

Cited by 117 publications

(41 citation statements)

References 17 publications

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“…This research team subsequently investigated acid, ester, and anhydride hydrogenation in some detail in studies which exclusively used Ru carbonyl clusters with monodentate trialkylphosphine ligands as catalysts. The reduction of succinic acid, (CH 2 CO 2 H) 2 with succinic anhydride, is compared in Table 15.13 [102].…”

Section: Hydrogenation Of Acids and Anhydridesmentioning

confidence: 99%

“…By using the [Ru 4 H 4 (CO) 8 (PnBu 3 ) 4 ] catalyst system reported for acid hydrogenation of acids [102], Matteoli and coworkers investigated the hydrogenation of dicarboxylic acid ester derivatives at 130 bar pressure and 180 8C [109]. Using relatively high catalyst loadings (maximum TON *150), DMO could be converted cleanly into the hydroxyl-ester, MG.…”

Section: Hydrogenation Of Acids and Anhydridesmentioning

confidence: 99%

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Homogeneous Hydrogenation of Aldehydes, Ketones, Imines and Carboxylic Acid Derivatives: Chemoselectivity and Catalytic Activity

Clarke¹,

Roff²

2006

The Handbook of Homogeneous Hydrogenation

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414Scheme 15.1 Hydrogenation of n-butyraldehyde. Table 15.1 Hydrogenation of aldehydes with [IrH 3 (PPh 3 ) 3 ] in acetic acid. Substrate Catalyst [mol.%] Temperature [8C] Yield [%] TON TOF [h -1 ] 0.022 80 73 3280 492 0.023 110 82 3540 177 0.032 90 64 2000 89 0.039 110 80 2030 81 0.013 110 98 7780 259 examined for a,b-unsaturated aldehydes (Scheme 15.2). Using the [IrH 3 (PPh 3 ) 3 ] complex in acetic acid for the hydrogenation of crotonaldehyde resulted in the formation of the saturated alcohol (Scheme 15.3). It was also noted that this catalyst did not allow for ketone hydrogenation at 10 bar. Other attempts to use iridium PPh 3 complexes such as [IrCl(PPh 3 ) 3 ], [IrCl(CO)(PPh 3 ) 2 ], [Ir(ClO 4 )(CO)(PPh 3 ) 2 ] and [Ir(CO)(PPh 3 ) 3 ]ClO 4 to hydrogenate unsaturated aldehydes did not yield great results [3], mainly because these catalysts suffered from low activity and selectivity.The catalytic system of [Ir(COD)Cl] 2 with an excess of the bulky phosphine P(o-MeOPh) 3 under transfer hydrogenation conditions of propan-2-ol and KOH was used successfully in the selective hydrogenation of cinnamaldehyde (Scheme 15.4) [4]. Selectivity and activity were found to increase with increasing P/Ir ratios, and complete conversion was achieved in as little as 5 minutes (turnover frequency (TOF) *6000 h -1 ). Hydrogenation of Aldehydes 415Scheme 15.2 Distribution of products in the hydrogenation of a,b-unsaturated aldehydes. Scheme 15.3 Hydrogenation of crotonaldehyde with [IrH 3 (PPh 3 ) 3 ] in acetic acid. Scheme 15.4 Transfer hydrogenation of cinnamaldehyde.Using molecular hydrogen as the reducing agent, [Ir(COD)(OCH 3 )] 2 with an excess of tertiary phosphine was better than [Ir(COD)Cl] 2 for the selective hydrogenation of cinnamaldehyde [5]. In these studies, a great dependence on solvent and ligand was reported. A variety of different phosphines, which were markedly different in their steric and electronic properties, were examined in this reaction. In propan-2-ol the most effective phosphine was PCy 2 Ph which gave 94% yield (TOF 235 h -1 ) of the unsaturated alcohol in a 2 h reaction under 30 bar H 2 at 100 8C. Phosphines such as PCyPh 2 , PPhPr i 2 , PPh 2 Pr i and PEtPh 2 were also effective in giving over 95% selectivity. The less-effective phosphines were PEt 2 Ph, PMePh 2 , PBu i 3 and PMe 2 Ph. Reactions that were performed in toluene were generally less effective.More recent advances in iridium-catalyzed aldehyde hydrogenation have been through the use of bidentate ligands [6]. In the hydrogenation of citral and cinnamaldehyde, replacing two triphenylphosphines in [IrH(CO)(PPh 3 ) 3 ] with bidentate phosphines BDNA, BDPX, BPPB, BISBI and PCP ( Fig. 15.1) led to an increase in catalytic activity. a) Selectivity of allylic alcohol formed as a percentage of total hydrogenation products. b) TOF (h -1 ) expressed for conversion of starting material. Hydrogenation of Aldehydes 419Scheme 15.5 Preparation of cationic DiPFc catalyst.

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Section: Hydrogenation Of Acids and Anhydridesmentioning

confidence: 99%

Section: Hydrogenation Of Acids and Anhydridesmentioning

confidence: 99%

Homogeneous Hydrogenation of Aldehydes, Ketones, Imines and Carboxylic Acid Derivatives: Chemoselectivity and Catalytic Activity

Clarke¹,

Roff²

2006

The Handbook of Homogeneous Hydrogenation

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“…Thus, Ru 2 (CO) 4 (OOCMe) 2 (PBu 3 ) 2 has been obtained from the reaction of H 4 Ru 4 (CO) 8 (PBu 3 ) 4 and acetic acid under hydrogen pressure [24].…”

Section: Synthetic Methodsmentioning

confidence: 99%

“…With acetic acid as substrate, ethyl acetate is obtained [Eq. (24)] exclusively at 180 • C and 130 bar (catalyst/substrate ratio 1:3600, conversion 37% after 24 h), the solution containing Ru 2 (CO) 4 (OOCMe) 2 (PBu 3 ) 2 ; dicarboxylic acids lead mainly to lactones [24]. The hydrogenation of dimethyl oxalate using Ru 2 (CO) 4 (25) Diruthenium tetracarbonyl complexes are also reported to catalyze carbonylation reactions.…”

Section: Catalytically Active Ru 2 (Co) 4 Complexesmentioning

confidence: 99%

Sawhorse-type diruthenium tetracarbonyl complexes

Therrien

Süß‐Fink

2009

Coordination Chemistry Reviews

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“…In this work, we synthesized new tetrahedral mono substituted carbonylhydride clusters with functional ized phosphine ligands H 2 RuOs 3 (CO) 12 (PS) (1) and H 4 Ru 4 (CO) 11 L (2)(3)(4)(5), where L = POx (2), PSug (3), PInd (4), and PStyr (5); PS is thienyldiphenylphosphine, POx is (1R,9R)[2(oxymethylquinolisidinyl)ethyl]di(2 phenylethyl)phosphine, PSug is (2 [5 (2,2 dimethyl 1,3 dioxolan 4 yl) 2,2 dimethyltetrahydrofuro[2,3 d] [1,3]di oxol 6 yl]oxyethyl)di(2 phenylethyl)phosphine, PInd is [2 (1 indolyl)propyl]di(2 phenylethyl)phosphine, PStyr is (2 phenylpropyl)distyrylphosphine. The structures of compounds 1-5 in solution were studied, and a model for the dynamic behavior of their coordination sphere was proposed.…”

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confidence: 99%

Structure and dynamic properties of substituted carbonylhydride clusters H2RuOs3(CO)13 and H4Ru4(CO)12 containing functionalized phosphines

et al. 2007

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The derivatives of the H 2 RuOs 3 (CO) 13 and H 4 Ru 4 (CO) 12 carbonylhydride clusters con taining functionalized (including chiral) phosphines were synthesized. The solid state struc ture of H 2 RuOs 3 (CO) 12 (Ph 2 P(C 4 H 3 S)) was determined by X ray diffraction analysis. The structures of other compounds in solution were determined using IR and 1 H and 31 P NMR spectroscopy. A study of the temperature dependences of the 1 H NMR spectra of the phos phine substituted tetrahedral clusters along with the analysis of literature data for their analogs showed that compounds of this type exist in solution as an equilibrium mixture of isomers, which differ in arrangement of the hydride ligands at the cluster skeleton. Interconversion of the isomeric forms is due to migration of the hydride ligands over the cluster skeleton. A general model for this dynamic process was proposed. The model is consistent with both our data and earlier results of other authors.Carbonylhydride clusters of the iron subgroup transi tion metals are used as efficient catalysts in hydrogena tion of unsaturated organic compounds. 1-4 From this point of view, it seems most attractive to consider phos phine substituted derivatives of the H 4 Ru 4 (CO) 12 and H 2 RuOs 3 (CO) 12 clusters, whose activity in various or ganic reactions is well known. 1-14 Reactions of asymmet ric synthesis 15 are especially interesting from the theoreti cal and applied viewpoints, and reactions of this type catalyzed by cluster compounds have been most poorly studied up to date, and only restricted examples of using the clusters in asymmetrical catalysis are available in the literature. 16-18As a rule, in the organometallic complexes of this type the hydride ligands participate in the low barrier dynamic processes, such as hydride migration over the cluster skeleton in solution 19-24 and even in the solid phase. 25-27 The fast intramolecular hydride exchange in the cluster compounds in solution has been evidenced for the first time for a series of compounds H 4 Ru 4 (CO) 12-x L x (L = P(OMe 3 ), x = 1-4). 28 However, subsequent more detailed studies 22,29 of the structure of the ligand environment and mechanism of dynamic processes in these compounds revealed no general pattern, and some conclusions of the above cited works even contradict each other.In this work, we synthesized new tetrahedral mono substituted carbonylhydride clusters with functional ized phosphine ligands H 2 RuOs 3 (CO) 12 (PS) (1) and H 4 Ru 4 (CO) 11 L (2-5), where L = POx (2), PSug (3), PInd (4), and PStyr (5); PS is thienyldiphenylphosphine, POx is (1R,9R)[2(oxymethylquinolisidinyl)ethyl]di(2 phenylethyl)phosphine, PSug is (2 [5 (2,2 dimethyl 1,3 dioxolan 4 yl) 2,2 dimethyltetrahydrofuro[2,3 d][1,3]di oxol 6 yl]oxyethyl)di(2 phenylethyl)phosphine, PInd is [2 (1 indolyl)propyl]di(2 phenylethyl)phosphine, PStyr is (2 phenylpropyl)distyrylphosphine. The structures of compounds 1-5 in solution were studied, and a model for the dynamic behavior of their coordination sphere was proposed.

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Homogeneous catalytic hydrogenation of free carboxylic acids in the presence of cluster ruthenium carbonyl hydrides

Cited by 117 publications

References 17 publications

Homogeneous Hydrogenation of Aldehydes, Ketones, Imines and Carboxylic Acid Derivatives: Chemoselectivity and Catalytic Activity

Homogeneous Hydrogenation of Aldehydes, Ketones, Imines and Carboxylic Acid Derivatives: Chemoselectivity and Catalytic Activity

Sawhorse-type diruthenium tetracarbonyl complexes

Structure and dynamic properties of substituted carbonylhydride clusters H2RuOs3(CO)13 and H4Ru4(CO)12 containing functionalized phosphines

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