HCOOH disproportionation to MeOH promoted by molybdenum PNP complexes.

Molybdenum(0) complexes with aliphatic aminophosphine pincer ligands have been prepared which are competent for the disproportionation of formic acid, thus representing the first example so far reported of non-noble metal species to catalytically promote such transformation. In general, formic acid disproportionation allows for an alternative access to methyl formate and methanol from renewable resources. MeOH selectivity up to 30% with a TON of 57 could be achieved while operating at atmospheric pressure. Selectivity (37%) and catalyst performance (TON = 69) could be further enhanced when the reaction was performed under hydrogen pressure (60 bars). A plausible mechanism based on experimental evidence is proposed.

Correction: HCOOH disproportionation to MeOH promoted by molybdenum PNP complexes.

[This corrects the article DOI: 10.1039/D1SC04181A.].

Cyclometalated Ruthenium Pincer Complexes as Catalysts for the α-Alkylation of Ketones with Alcohols.

Ruthenium PNP pincer complexes bearing supplementary cyclometalated C,N-bound ligands have been prepared and fully characterized for the first time. By replacing CO and H- as ancillary ligands in such complexes, additional electronic and steric modifications of this topical class of catalysts are possible. The advantages of the new catalysts are demonstrated in the general α-alkylation of ketones with alcohols following a hydrogen autotransfer protocol. Herein, various aliphatic and benzylic alcohols were applied as green alkylating agents for ketones bearing aromatic, heteroaromatic or aliphatic substituents as well as cyclic ones. Mechanistic investigations revealed that during catalysis, Ru carboxylate complexes are predominantly formed whereas neither the PNP nor the CN ligand are released from the catalyst in significant amounts.

Efficient and selective hydrogenation of amides to alcohols and amines using a well-defined manganese-PNN pincer complex.

Novel well-defined NNP and PNP manganese pincer complexes have been synthetized and fully characterized. The catalyst Mn-2 containing an imidazolyaminolphosphino ligand shows high activity and selectivity in the hydrogenation of a wide range of secondary and tertiary amides to the corresponding alcohols and amines, under relatively mild conditions. For the first time, more challenging substrates like primary aromatic amides including an actual herbicide can also be hydrogenated using this earth-abundant metal-based pincer catalyst.

Unravelling the Mechanism of Basic Aqueous Methanol Dehydrogenation Catalyzed by Ru-PNP Pincer Complexes.

Ruthenium PNP complex 1a (RuH(CO)Cl(HN(C2H4Pi-Pr2)2)) represents a state-of-the-art catalyst for low-temperature (<100 °C) aqueous methanol dehydrogenation to H2 and CO2. Herein, we describe an investigation that combines experiment, spectroscopy, and theory to provide a mechanistic rationale for this process. During catalysis, the presence of two anionic resting states was revealed, Ru-dihydride (3-) and Ru-monohydride (4-) that are deprotonated at nitrogen in the pincer ligand backbone. DFT calculations showed that O- and CH- coordination modes of methoxide to ruthenium compete, and form complexes 4- and 3-, respectively. Not only does the reaction rate increase with increasing KOH, but the ratio of 3-/4- increases, demonstrating that the "inner-sphere" C-H cleavage, via C-H coordination of methoxide to Ru, is promoted by base. Protonation of 3- liberates H2 gas and formaldehyde, the latter of which is rapidly consumed by KOH to give the corresponding gem-diolate and provides the overall driving force for the reaction. Full MeOH reforming is achieved through the corresponding steps that start from the gem-diolate and formate. Theoretical studies into the mechanism of the catalyst Me-1a (N-methylated 1a) revealed that C-H coordination to Ru sets-up C-H cleavage and hydride delivery; a process that is also promoted by base, as observed experimentally. However, in this case, Ru-dihydride Me-3 is much more stable to protonation and can even be observed under neutral conditions. The greater stability of Me-3 rationalizes the lower rates of Me-1a compared to 1a, and also explains why the reaction rate then drops with increasing KOH concentration.

NNP-Type Pincer Imidazolylphosphine Ruthenium Complexes: Efficient Base-Free Hydrogenation of Aromatic and Aliphatic Nitriles under Mild Conditions.

A series of seven novel N(Im)N(H)P-type pincer imidazolylphosphine ruthenium complexes has been synthesized and fully characterized. The use of hydrogenation of benzonitrile as a benchmark test identified [RuHCl(CO)(N(Im)N(H) P(tBu))] as the most active catalyst. With its stable Ru-BH4 analogue, in which chloride is replaced by BH4, a broad range of (hetero)aromatic and aliphatic nitriles, including industrially interesting adiponitrile, has been hydrogenated under mild and base-free conditions.

A comparative computationally study about the defined M(II) pincer hydrogenation catalysts (M = Fe, Ru, Os).

The mechanism of acetonitrile and methyl benzoate catalytic hydrogenation using pincer catalysts M(H)2 (CO)[NH(C2 H4 PiPr2 )2 ] (1M) and M(H)(CO)[N(C2 H4 PiPr2 )2 ] (2M) (M = Fe, Ru, Os) has been computed at various levels of density functional theory. The computed equilibrium between 1Fe and 2Fe agrees perfectly with the experimental observations. On the basis of the activation barriers and reaction energies, the best catalysts for acetonitrile hydrogenation are 1Fe/2Fe and 1Ru/2Ru, and the best catalysts for methyl benzoate hydrogenation are 1Ru/2Ru. The best catalysts for the dehydrogenation of benzyl alcohol are 1Ru/2Ru. It is to note that the current polarizable continuum model is not sufficient in modeling the solvation effect in the energetic properties of these catalysts as well as their catalytic properties in hydrogenation reaction, as no equilibrium could be established between 1Fe and 2Fe. Comparison with other methods and procedures has been made. © 2015 Wiley Periodicals, Inc.

Towards a general ruthenium-catalyzed hydrogenation of secondary and tertiary amides to amines.

A broad range of secondary and tertiary amides has been hydrogenated to the corresponding amines under mild conditions using an in situ catalyst generated by combining [Ru(acac)3], 1,1,1-tris(diphenylphosphinomethyl)ethane (Triphos) and Yb(OTf)3. The presence of the metal triflate allows to mitigate reaction conditions compared to previous reports thus improving yields and selectivities in the desired amines. The excellent isolated yields of two scale-up experiments corroborate the feasibility of the reaction protocol. Control experiments indicate that, after the initial reduction of the amide carbonyl group, the reaction proceeds through the reductive amination of the alcohol with the amine arising from collapse of the intermediate hemiaminal.

Mild and selective hydrogenation of aromatic and aliphatic (di)nitriles with a well-defined iron pincer complex.

The catalytic hydrogenation of carboxylic acid derivatives represents an atom-efficient and clean reduction methodology in organic chemistry. More specifically, the selective hydrogenation of nitriles offers the possibility for a green synthesis of valuable primary amines. So far, this transformation lacks of useful, broadly applicable non-noble metal-based catalyst systems. In the present study, we describe a molecular-defined iron complex, which allows for the hydrogenation of aryl, alkyl, heterocyclic nitriles and dinitriles. By using an iron PNP pincer complex, we achieve very good functional group tolerance. Ester, ether, acetamido as well as amino substituents are not reduced in the presence of nitriles. Moreover, nitriles including an α,ß-unsaturated double bond and halogenated derivatives are well tolerated in this reaction. Notably, our complex constitutes the first example of an homogeneous catalyst, which permits the selective hydrogenation of industrially important adipodinitrile to 1,6-hexamethylenediamine.

Hydrogenation of esters to alcohols with a well-defined iron complex.

We present the first base-free Fe-catalyzed ester reduction applying molecular hydrogen. Without any additives, a variety of carboxylic acid esters and lactones were hydrogenated with high efficiency. Computations reveal an outer-sphere mechanism involving simultaneous hydrogen transfer from the iron center and the ligand. This assumption is supported by NMR experiments.

Selective hydrogen production from methanol with a defined iron pincer catalyst under mild conditions.

Molecularly well-defined iron pincer complexes promote the aqueous-phase reforming of methanol to carbon dioxide and hydrogen, which is of interest in the context of a methanol and hydrogen economy. For the first time, the use of earth-abundant iron complexes under mild conditions for efficient hydrogen generation from alcohols is demonstrated.

Low-temperature aqueous-phase methanol dehydrogenation to hydrogen and carbon dioxide.

Hydrogen produced from renewable resources is a promising potential source of clean energy. With the help of low-temperature proton-exchange membrane fuel cells, molecular hydrogen can be converted efficiently to produce electricity. The implementation of sustainable hydrogen production and subsequent hydrogen conversion to energy is called "hydrogen economy". Unfortunately, its physical properties make the transport and handling of hydrogen gas difficult. To overcome this, methanol can be used as a material for the storage of hydrogen, because it is a liquid at room temperature and contains 12.6 per cent hydrogen. However, the state-of-the-art method for the production of hydrogen from methanol (methanol reforming) is conducted at high temperatures (over 200 degrees Celsius) and high pressures (25-50 bar), which limits its potential applications. Here we describe an efficient low-temperature aqueous-phase methanol dehydrogenation process, which is facilitated by ruthenium complexes. Hydrogen generation by this method proceeds at 65-95 degrees Celsius and ambient pressure with excellent catalyst turnover frequencies (4,700 per hour) and turnover numbers (exceeding 350,000). This would make the delivery of hydrogen on mobile devices--and hence the use of methanol as a practical hydrogen carrier--feasible.

Stereospecific synthesis and catalytic activity of L-histidylidene metal complexes.

We report on the synthesis, metal coordination, and catalytic impact of histidylidene, a histidine-derived N-heterocyclic carbene (NHC) ligand. The histidinium salt 3, comprising methyl substituents at both heterocyclic nitrogens and protected at the C- and N-terminus of the amino acid, was rhodated and iridated by a transmetallation protocol using Ag(2)O. Ambient temperature and short reaction times were pivotal for full retention of configuration at the α-carbon. The stereospecificity of the reaction was conveniently probed by (31)P NMR spectroscopy after transmetallation with rhodium(I) and coordination of enantiopure (S)-Ph-binepine. The histidylidene rhodium complexes are highly efficient catalysts for the mild hydrosilylation of ketones. For the cationic complexes [Rh(cod)(histidylidene)(phosphine)](+), lowering the temperature shifted the rate-limiting step of the catalytic reaction to an earlier stage that is not enantioselective. Hence the asymmetric induction-which is governed by the chiral phosphine-did not improve at low temperature.

Captured at last: a catalyst-substrate adduct and a Rh-dihydride solvate in the asymmetric hydrogenation by a Rh-monophosphine catalyst.

The mechanism of asymmetric hydrogenation catalyzed by [Rh(NBD)((R)-PhenylBinepine)(2)]SbF(6)1 has been studied by NMR experiments and DFT computations. Either the low-temperature hydrogenation of the catalyst-substrate adduct 4 or the reaction of solvate dihydride 6 with MAC produced the hydrogenation product with over 99% ee (S).

Unravelling the reaction path of rhodium-MonoPhos-catalysed olefin hydrogenation.

The mechanism of the asymmetric hydrogenation of methyl (Z)-2-acetamidocinnamate (mac) catalysed by [Rh(MonoPhos)(2)(nbd)]SbF(6) (MonoPhos: 3,5-dioxa-4-phosphacyclohepta[2,1-a:3,4-a']dinaphthalen-4-yl)dimethylamine) was elucidated by using (1)H, (31)P and (103)Rh NMR spectroscopy and ESI-MS. The use of nbd allows one to obtain in pure form the rhodium complex that contains two units of the ligand. In contrast to the analogous complexes that contain cis,cis-1,5-cyclooctadiene (cod), this complex shows well-resolved NMR spectroscopic signals. Hydrogenation of these catalyst precursors at 1 bar total pressure gave rise to the formation of a bimetallic complex of general formula [Rh(MonoPhos)(2)](2)(SbF(6))(2); no solvate complexes were detected. In the dimeric complex both rhodium atoms are ligated to two MonoPhos ligands but, in addition, each rhodium atom also binds to one of the binaphthyl rings of a ligand that is bound to the other rhodium metal. Upon addition of mac, a mixture of diastereomeric complexes [Rh(MonoPhos)(2)(mac)]SbF(6) is formed in which the substrate is bound in a chelate fashion to the metal. Upon hydrogenation, these adducts are converted into a new complex [Rh(MonoPhos)(2){mac(H)(2)}]SbF(6) in which the methyl phenylalaninate mac(H)(2) is bound through its aromatic ring to rhodium. Addition of mac to this complex leads to displacement of the product by the substrate. No hydride intermediates could be detected and no evidence was found for the involvement at any stage of the process of complexes with only one coordinated MonoPhos. The collected data suggest that the asymmetric hydrogenation follows a Halpern-like mechanism in which the less abundant substrate-catalyst adduct is preferentially hydrogenated to phenylalanine methyl ester.

BINEPINES: chiral binaphthalene-core monophosphepine ligands for multipurpose asymmetric catalysis.

The atropisomeric structure of 4,5-dihydro-3H-dinaphtho[2,1-c;1',2'-e]phosphepine is the common axially chiral scaffold of a library of monophosphine ligands nicknamed BINEPINES that have shown a quite remarkable stereoselection efficiency in a broad variety of enantioselective reactions involving the formation of new C-H or C-C or C-X bonds. In this critical review the properties and scope of this type of chiral ligands are illustrated (70 references).

Asymmetric transfer hydrogenation: chiral ligands and applications.

Hydrogen transfer reduction processes are attracting increasing interest from synthetic chemists in view of their operational simplicity and high selectivity. In this tutorial review the most significant advances recently achieved in the stereoselective reduction of unsaturated organic compounds catalyzed by homogeneous transition metal complexes are critically reviewed. A sharp growth of the synthetic applications of this technique in the synthesis of fine chemicals is predictable as the use of transition metal catalyzed reactions will become more familiar to synthetic chemists.

Intravenous administration of the food-derived opioid peptide gluten exorphin B5 stimulates prolactin secretion in rats.

Gluten Exorphin B5 (GE-B5) is a food-derived opioid peptide, identified in vitro in enzymatic digests of wheat gluten. It has been suggested that this peptide may play a regulatory role on pituitary secretion, since it stimulates prolactin (PRL) secretion when administered in the cerebral ventricles in rats. It is not known, however, if GE-B5 can exert this stimulatory action after peripheral administration. In order to clarify this aspect, we gave the following treatments to four groups of male rats: intravenous (i.v.) vehicle, GE-B5 3 mg/kg body weight i.v., naloxone intraperitoneally (i.p.) followed by vehicle i.v., naloxone i.p. followed by GE-B5 i.v. Blood samples for PRL were taken at intervals for 60 min after vehicle or GE-B5 administration. At the dose of 3 mg/kg body weight, GE-B5 induced a significant increase in PRL levels; naloxone completely abolished any effect of GE-B5 on PRL secretion. The present study indicates that GE-B5 stimulates PRL secretion after peripheral administration and that its action is mediated via classical opioid receptors; moreover, it identifies the minimum peptide dose which must reach the blood in order to exert its action on PRL secretion.