Phosphite‐Derivatized Ruthenium‐Carbohydrate Complexes in the Catalytic Hydration of Nitriles. Short Communication

Ashraf, Shaheen M.; Berger, Ingeborg; Nazarov, Alexey A.; Hartinger, Christian G.; Koroteev, M. P.; Нифантьев, Э. Е.; Keppler, Bernhard K.

doi:10.1002/cbdv.200890151

Cited by 21 publications

(9 citation statements)

References 21 publications

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“…9) have been tested as catalysts for the selective hydration of chloroacetonitriles Cl 3−n CH n CuN (n = 0, 1, 2) into the corresponding chloroacetamides Cl 3−n CH n C(vO)NH 2 in water. 66 All of them were found to be active, leading, with metal loadings of 0.1-0.2 mol%, to conversions of up to 58% after 24 h of heating at 75 °C.…”

Section: Other Hydrophilic P-donor Ligandsmentioning

confidence: 97%

Arene-ruthenium(ii) complexes with hydrophilic P-donor ligands: versatile catalysts in aqueous media

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Cadierno

2014

Dalton Trans.

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In the last few years there has been increasing interest in the use of water as a reaction medium for catalysis, and therefore in designing water-soluble transition-metal catalysts. Half-sandwich (η(6)-arene)-ruthenium(ii) complexes are a versatile and well-known family of ruthenium compounds that exhibit a rich catalytic and coordination chemistry. This Perspective article focuses on the catalytic applications in aqueous media of (η(6)-arene)-ruthenium(ii) complexes containing water-soluble phosphines, and related hydrophilic P-donor ligands.

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Section: Other Hydrophilic P-donor Ligandsmentioning

confidence: 97%

Arene-ruthenium(ii) complexes with hydrophilic P-donor ligands: versatile catalysts in aqueous media

Crochet

Cadierno

2014

Dalton Trans.

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“…Addition of pentane afforded 80 mg (73%) of a white solid. 13 C NMR, CDCl 3 , δ, ppm: 166 (ipso C); 158 (CO); 157 (ipso C); 148 (ipso C); 147 (ipso C); 137 (CH); 135 (CH); 125 (CH); 122 (CH); 121 (CH); 120 (CH); 59 (CH 2 ); 58 (CH 2 ). 1 H NMR analysis of the residues of the mother liquor showed that some ligand was still present in good amount in the sample.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Steric Congestion at, and Proximity to, a Ferrous Center Leads to Hydration of α-Nitrile Substituents Forming Coordinated Carboxamides

et al. 2014

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The question of the conversion of nitrile groups into amides (nitrile hydration) by action of water in mild and eco-compatible conditions and in the presence of iron is addressed in this article. We come back to the only known example of hydration of a nitrile function into carboxamide by a ferrous [Fe(II)] center in particularly mild conditions and very efficiently and demonstrate that these unusual conditions result from the occurrence of steric stress at the reaction site and formation of a more stable end product. Two bis(cyano-substituted) (tris 2-pyridyl methyl amine) ligands have been prepared, and the structures of the corresponding FeCl2 complexes are reported, both in the solid state and in solution. These two ligands only differ by the position of the nitrile group on the tripod in the α and β position, respectively, with respect to the pyridine nitrogen. In any case, intramolecular coordination is impossible. Upon action of water, the nitrile groups are hydrated however only if they are located in the α position. The fact that the β-substituted β-(NC)2TPAFeCl2 complex is not water sensitive suggests that the reaction proceeds in an intramolecular way at the vicinity of the metal center. In the bis α-substituted α-(NC)2TPAFeCl2 complex, both functions are converted in a very clean fashion, pointing out that this complex exhibits ligand flexibility and is not deactivated after the first hydration. At a preparative scale, this reaction allows the one-pot conversion of the bis(cyano-substituted) tripod into a bis(amido-substituted) one in particularly mild conditions with a very good yield. Additionally, the XRD structure of a ferric compound in which the two carboxamido ligands are bound to the metal in a seven-coordinate environment is reported.

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“…With this mechanistic idea in mind, and continuing with our interest in this key catalytic transformation, , we wondered about the potential of (η 6 -arene)-Ru(II) complexes A − C , containing readily accessible amino-phosphine ligands (Figure ), as catalysts for the selective hydration of nitrile to amides . We reasoned that, while the presence of a pendant amino group on these P-donor ligands would ensure the activation of the water molecule via hydrogen bonding, the exact location of the amino substituent on the aromatic ring should drastically affect the efficiency of these catalysts, conditioning the effective approach of the activated hydrogen-bonded water molecule to the coordinated nitrile.…”

Section: Introductionmentioning

confidence: 99%

Arene−Ruthenium(II) Complexes Containing Amino−Phosphine Ligands as Catalysts for Nitrile Hydration Reactions

et al. 2010

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Three different series of novel mononuclear arene-ruthenium(II) complexes containing aminophosphine ligands, namely, [RuCl 2 {κ 1 (P)-2-Ph 2 PC 6 H 4 CH 2 NHR}(η 6 -arene)], [RuCl 2 {κ 1 (P)-3-Ph 2 -PC 6 H 4 CH 2 NHR}(η 6 -arene)], and [RuCl 2 {κ 1 (P)-4-Ph 2 PC 6 H 4 CH 2 NHR}(η 6 -arene)] (arene = C 6 H 6 , p-cymene, 1,3,5-C 6 H 3 Me 3 , C 6 Me 6 ; R = i Pr, t Bu; all combinations), have been synthesized and fully characterized. These readily accessible species are efficient catalysts for the selective hydration of organonitriles into amides under challenging reaction conditions, i.e., pure aqueous medium in the absence of any cocatalyst, being much more active than their corresponding nonfunctionalized triphenylphosphine counterparts [RuCl 2 (PPh 3 )(η 6 -arene)]. The results obtained in this study indicate that the (amino-phosphine)ruthenium(II) complexes operate through a "bifunctional catalysis" mechanism in which the ruthenium center acts as a Lewis acid, activating the nitrile molecule, and the P-donor ligand acts as a Brønsted base, the pendant amino group generating the real nucleophile of the hydration process, i.e., the OHgroup.

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Phosphite‐Derivatized Ruthenium‐Carbohydrate Complexes in the Catalytic Hydration of Nitriles. Short Communication

Cited by 21 publications

References 21 publications

Arene-ruthenium(ii) complexes with hydrophilic P-donor ligands: versatile catalysts in aqueous media

Arene-ruthenium(ii) complexes with hydrophilic P-donor ligands: versatile catalysts in aqueous media

Steric Congestion at, and Proximity to, a Ferrous Center Leads to Hydration of α-Nitrile Substituents Forming Coordinated Carboxamides

Arene−Ruthenium(II) Complexes Containing Amino−Phosphine Ligands as Catalysts for Nitrile Hydration Reactions

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