Valorisation of plastic waste via metal-catalysed depolymerisation.

Metal-catalysed depolymerisation of plastics to reusable building blocks, including monomers, oligomers or added-value chemicals, is an attractive tool for the recycling and valorisation of these materials. The present manuscript shortly reviews the most significant contributions that appeared in the field within the period January 2010-January 2020 describing selective depolymerisation methods of plastics. Achievements are broken down according to the plastic material, namely polyolefins, polyesters, polycarbonates and polyamides.

Biomass-derived chemical substitutes for bisphenol A: recent advancements in catalytic synthesis.

Bisphenol A is an oil-derived, large market volume chemical with a wide spectrum of applications in plastics, adhesives and thermal papers. However, bisphenol A is not considered safe due to its endocrine disrupting properties and reproductive toxicity. Several functional substitutes of bisphenol A have been proposed in the literature, produced from plant biomass.

Continuous-Flow Oxidation of HMF to FDCA by Resin-Supported Platinum Catalysts in Neat Water.

The oxidation reaction of 5-hydroxymethylfurfural to the bioplastic monomer 2,5-furandicarboxylic acid over heterogenous resin-supported Pt catalysts was investigated in detail, under continuous flow, base-free conditions, and in neat water. The product was continuously obtained in 99 % yield by running the reaction at 120 °C, 303 s residence time, 1.2 mL min O flow rate, and 7.

Low-Temperature Continuous-Flow Dehydration of Xylose Over Water-Tolerant Niobia-Titania Heterogeneous Catalysts.

The sustainable conversion of vegetable biomass-derived feeds to useful chemicals requires innovative routes meeting environmental and economical criteria. The approach herein pursued is the synthesis of water-tolerant, unconventional solid acid monolithic catalysts based on a mixed niobia-titania skeleton building up a hierarchical open-cell network of meso- and macropores, and tailored for use under continuous-flow conditions. The materials were characterized by spectroscopic, microscopy, and diffraction techniques, showing a reproducible isotropic structure and an increasing Lewis/Brønsted acid sites ratio with increasing Nb content.

Continuous-flow processes for the catalytic partial hydrogenation reaction of alkynes.

The catalytic partial hydrogenation of substituted alkynes to alkenes is a process of high importance in the manufacture of several market chemicals. The present paper shortly reviews the heterogeneous catalytic systems engineered for this reaction under continuous flow and in the liquid phase. The main contributions appeared in the literature from 1997 up to August 2016 are discussed in terms of reactor design.

Selective hydrogenation over Pd nanoparticles supported on a pore-flow-through silica monolith microreactor with hierarchical porosity.

Well-dispersed Pd nanoparticles have been synthesized inside the mesoporosity of a silica monolith featuring hierarchical porosity of homogeneous interconnected macropores (4 microns) and mesopores (11 nm). These monoliths have been implemented as microreactors for selective hydrogenation reactions. Conversion and selectivity can be tuned by adjusting the flow rates of hydrogen and substrates.

Green production of polymer-supported PdNPs: application to the environmentally benign catalyzed synthesis of cis-3-hexen-1-ol under flow conditions.

Pd nanoparticles generated on gel type ion-exchange resins under catalytic conditions show high activity, selectivity and durability in partial hydrogenation reactions under mild conditions, thus providing a green, low-cost option for fine-chemicals production. The application to the continuous-flow synthesis of the leaf alcohol fragrance cis-3-hexen-1-ol is demonstrated.

Iodine activation of coordinated white phosphorus: formation and transformation of 1,3-dihydride-2-iodidecyclotetraphosphane.

Double stabilization: Previously unknown polyphosphorus compounds are obtained by activation of white phosphorus (P(4)) coordinated between two CpRu(PPh(3))(2) moieties with iodine, and subsequent hydrolysis. The polyphosphorus compounds (P(4) H(2) I, P(4) H(2), P(3) H(5); see scheme, Cp=cyclopentadienyl) are all stabilized by coordination to two ruthenium centers.

Emerging strategies in sustainable fine-chemical synthesis: asymmetric catalysis by metal nanoparticles.

The combination of chiral- and nano-technologies is potentially one of the most promising strategies for "green" catalytic conversions aimed at fine-chemical production. This paper reviews the most representative examples and highlights recent achievements in the field of enantioselective processes catalyzed by metal nanoparticles (MNPs), with a view to the potential of the methodology and future perspectives. Applications are described according to the nanocatalyst type used, either liquid-phase suspensions or solid-supported systems.

Getting a clue to the hydrolytic activation of white phosphorus: the generation and stabilization of P(OH)2PHPHPH(OH) at ruthenium centers.

The bimetallic compound [{CpRu(PPh(3))(2)}(2)(mu,eta(1:1)-P(4))][CF(3)SO(3)](2), in which the tetrahedral P(4) is bound to two CpRu(PPh(3))(2) fragments, slowly reacts under mild conditions with a moderate excess of water (1:20) to yield a mixture of compounds. Among the hydrolysis products, the new, remarkably stable complexes [{CpRu(PPh(3))}{CpRu(PPh(3))(2)}{mu(1,4:3),eta(2:1)-P(OH)(2)PHPHPH(OH)}](CF(3)SO(3))(2) (2) and [{CpRu(PPh(3))(2)}{CpRu(PPh(3)){P(OH)(3))}(mu,eta(1:1)-P(2)H(4))](CF(3)SO(3))(2) (3) have been isolated. In the former, the previously unknown 1,1,4-tris(hydroxy)tetraphosphane molecule, P(OH)(2)PHPHPH(OH), is 1,4- and, respectively, 3-coordinated to the CpRu(PPh(3)) and the CpRu(PPh(3))(2) moieties; in the latter, the diphosphane P(2)H(4) is stabilized through coordination to two different metal fragments.

NMR studies on the novel heterobimetallic complexes [M(dppm)(Ph(2)PCH(2)PPh(2)PPPP) {Pt(PPh3)2}]OTf (M = Rh, Ir) derived from the stepwise activation of white phosphorus.

The solution structures of the novel heterobimetallic complexes [Ir(dppm)(Ph(2)PCH(2)PPh(2)PPPP){Pt(PPh(3))2}]OTf and [Rh(dppm)(Ph(2)PCH(2)PPh(2)PPPP){Pt(PPh(3))(2)}]OTf derived from the reaction of Rh and Ir--P(5) precursors with [Pt(C2H4)(PPh3)2] have been unambiguously assigned on the basis of 1H NMR and 31P{1H} NMR data. The results are in agreement with the regio-selective insertion of the {Pt(PPh3)2} moiety resulting in a new pentaphosphorus topology which agrees with the formal formation of a unique phosphonium(+)-tetraphosphabutadienide(2-) ligand.

Collective headgroup conformational transition in twisted micellar superstructures.

Predictions on amphiphilic self-assemblies traditionally rely on considerations on molecular shape and charge of the surfactant. In the case of functional surfactants a more sophisticated toolbox becomes necessary to design amphiphiles encoding chemical functionalities that provide additional responsive properties to their self-assemblies. Here we report on a comprehensive and combined structural-spectroscopic characterization of 1,2-dilauroyl-phosphatidyl-adenosine (DLPA) micelles in phosphate buffer.

Hydrolysis of dinuclear ruthenium complexes [{CpRu(PPh3)2}2(micro,eta(1:1)-L)][CF3SO3]2 (L=P4, P4S3): simple access to metal complexes of P2H4 and PH2SH.

The reaction of [CpRu(PPh(3))(2)Cl] (1) with half an equivalent of P(4) or P(4)S(3) in the presence of AgCF(3)SO(3) as chloride scavenger affords the stable dimetal complexes [{CpRu(PPh(3))(2)}(2)(micro,eta(1:1)-P(4))][CF(3)SO(3)](2).3 CH(2)Cl(2) (2) and [{CpRu(PPh(3))(2)}(2)(micro,eta(1:1)-P(apical)-P(basal)-P(4)S(3))][CF(3)SO(3)](2).0.

Hydrogenation of arenes over silica-supported catalysts that combine a grafted rhodium complex and palladium nanoparticles: evidence for substrate activation on Rh(single-site)-Pd(metal) moieties.

The complex Rh(cod)(sulfos) (Rh(I); sulfos = (-)O(3)S(C(6)H(4))CH(2)C(CH(2)PPh(2))(3); cod = cycloocta-1,5-diene), either free or supported on silica, does not catalyze the hydrogenation of benzene in either homogeneous or heterogeneous phase. However, when silica contains supported Pd metal nanoparticles (Pd(0)/SiO(2)), a hybrid catalyst (Rh(I)-Pd(0)/SiO(2)) is formed that hydrogenates benzene 4 times faster than does Pd(0)/SiO(2) alone. EXAFS and DRIFT measurements of in situ and ex situ prepared samples, batch catalytic reactions under different conditions, deuterium labeling experiments, and model organometallic studies, taken together, have shown that the rhodium single sites and the palladium nanoparticles cooperate with each other in promoting the hydrogenation of benzene through the formation of a unique entity throughout the catalytic cycle.

Recycling asymmetric hydrogenation catalysts by their immobilization onto ion-exchange resins.

Ion-exchange resins can be used as supports for the preparation of single-site, heterogenised asymmetric hydrogenation catalysts. The immobilised catalysts obtained can be efficiently and conveniently recovered and recycled. This article reviews the significant contributions in the field including the main concepts behind the design and the applications of this type of catalyst.

Recycling asymmetric hydrogenation catalysts by their immobilisation onto ion-exchange resins.

New systems based on cationic chiral phosphine-rhodium complexes anchored to a commercial cation-exchange gel-type resin showed high efficiency and easy recycling in the asymmetric hydrogenation of prochiral olefins.

Synthesis, characterisation and molecular structure of Re(III) 2-oxacyclocarbenes stabilised by a benzoyldiazenido ligand.

A family of new Fischer-type rhenium(III) benzoyldiazenido-2-oxacyclocarbenes of formula [(ReCl2[eta1-N2C(O)Ph][=C(CH2)nCH(R)O](PPh3)2][n = 2, R = H (2), R = Me (3); n = 3, R = H (4), R = Me (5)] have been prepared by reaction of [ReCl2[eta2-N2C(Ph)O](PPh3)2] (1) with omega-alkynols, such as 3-butyn-1-ol, 4-pentyn-1-ol, 4-pentyn-2-ol, 5-hexyn-2-ol in refluxing THF. The correct formulation of the carbene derivatives 2-5 has been unambiguously determined in solution by NMR analysis and confirmed for compounds 2-4 by X-ray diffraction methods in the solid state. All complexes are octahedral with the benzoyldiazenido ligand, Re[N2C(O)Ph], adopting a "single bent" conformation.

Activation and functionalization of white phosphorus at rhodium: experimental and computational analysis of the [(triphos)Rh (eta1:eta2-P4RR')]Y complexes (triphos=MeC(CH2PPh2)3; R=H, Alkyl, Aryl; R'=2 electrons, H, Me).

Thermal reaction of white phosphorus with [(triphos)RhH(3)] (1) in THF affords [(triphos)Rh(eta(1):eta(2)-P(4)H)] (2), triphos=MeC(CH(2)PPh(2))(3). Similar complexes [(triphos)Rh(eta(1):eta(2)-P(4)R)] (R=Me (7), Et (8), Ph (9)) also form at lower temperature by the reaction of P(4) and [(triphos)Rh(R)(eta(2)-C(2)H(4))] with elimination of ethene. In contrast, a double-insertion process follows the reaction of [(triphos)Rh(H)(eta(2)-C(2)H(4))] and P(4) to generate tetraphosphido ethyl complex 8.

The first tridentate phosphine ligand combining planar, phosphorus and carbon chirality.

Two new diastereomerically pure tridentate phosphine ligands combining planar, phosphorus and carbon chirality have been conveniently synthesized via resolution of their phosphineoxide-diborane adducts and structurally characterized by X-ray analyses.

Dioxomolybdenum(VI) Complexes with New Enantiomerically Pure Amino Diol Ligands.

(R)-Phenylglycinol is shown to be an efficient building block for the synthesis of chiral amino diols in pure diastereomeric form by epoxide ring-opening reactions. The reaction with rac-trans-stilbene oxide gives [HOCH(2)-(R)-PhCH]NH[(S)-PhCH-(R)-PhCHOH] [2(R)-3(R)-4(S)-HNO(2)H(2)] in 32% yield, which can be methylated at nitrogen to give enantiomerically pure [HOCH(2)-(R)-PhCH]NCH(3)[(S)-PhCH-(R)-PhCHOH] [2(R)-3(R)-4(S)-MeNO(2)H(2)]. These amino diol ligands have been used to prepare chiral dioxomolybdenyl complexes of the formula N(R)-2(R)-3(R)-4(S)-(HNO(2))MoO(2) (1) and N(R)-2(R)-3(R)-4(S)-(MeNO(2))MoO(2) (2).