The Tishchenko reaction mediated by organo-f-complexes: the myths and obstacles.

For over a century, the Tishchenko reaction has been a valuable technique for synthesizing esters from aldehydes, serving a variety of applications in different domains. Beyond the remarkable advances in organoactinide and organolanthanide chemistry over the past two decades, there has been a significant increase in the research of the electrophilic d0/fn chemistry of organoactinide and organolanthanide compounds due to the captivating interplay between their structure and reactivity, and their exceptional performance in various homogeneous catalytic processes. The remarkable influence of ligand design, both in terms of steric hindrance and electronic properties, on the catalytic activity of organo-f-element complexes in organic transformations is well-established. However, the traditional view was that the significant oxophilicity of actinide and lanthanide complexes makes them unfavorable for reactions involving oxygen because of catalytic poisoning and their applications have been relatively limited, primarily focused on hydroalkoxylation, small-molecule activation, and cyclic ester polymerization. This review dissects the intricate interplay between ligand design and catalytic activity in actinide and lanthanide complexes, specifically in the context of the Tishchenko esterification.

Temperature Dependence of the Ring Opening of Cyclopropene Imines on Thorium Metallocenes.

The reactions of two highly strained cyclopropenimine ligands L1H and L2H (L1H = N1,N1,N2,N2-tetraisopropyl-3-iminocycloprop-1-ene-1,2-diamine, L2H = N1,N1,N2,N2-tetracyclohexyl-3-iminocycloprop-1-ene-1,2-diamine) with three thorium precursors Cp*2ThCl2, Cp*2Th(Cl)(CH3), and Cp*2Th(CH3)2 were studied. At -20 °C, L1H and L2H react with Cp*2ThCl2 to form Th1 (Th1 = Cp*2ThCl2(L1H)) and Th2 (Th2 = Cp*2ThCl2(L2H)), respectively, where the neutral ligand coordinates to the thorium metal center. Coordination of the ligand to the thorium metal center introduces aromaticity at the cyclopropene ring of the ligand. Reaction at room temperature results in the ring opening of the ligand to form Th3 (Th3 = Cp*2ThCl2((Z)-2,3-bis(diisopropylamino)acrylonitrile) and Th4 (Th4 = Cp*2ThCl2((Z)-2,3-bis(dicyclohexylamino)acrylonitrile), where the cyclopropenimine converts into a nitrile and coordinates to the thorium metal center. Reaction of L1H and L2H with Cp*2Th(Cl)(CH3) and/or Cp*2Th(CH3)2 at -20 °C results in a rapid methanolysis reaction and forms Cp*2Th(L1/L2)(CH3/Cl)-type complexes Th5 (Th5 = Cp*2Th(L1)(CH3)), Th6 (Th6 = Cp*2Th(L2)(CH3), Th7 (Th7 = Cp*2Th(L1)(Cl), and Th8 (Th8 = Cp*2Th(L2)(Cl). On the other hand, at room temperature, these reactions result in a ring opening of the ligand. Room-temperature reaction of L1H and L2H with Cp*2Th(CH3)2 results in Th9 (Th9 = Cp*2Th(CH3)((Z)-3-imino-N1,N1,N2,N2-tetraisopropylbut-1-ene-1,2-diamine) and Th10 (Th10 = Cp*2Th(CH3)((Z)-3-imino-N1,N1,N2,N2-tetracyclohexylbut-1-ene-1,2-diamine). Similarly, at room temperature, L1H and L2H react with Cp*2Th(Cl)(CH3) to form Th11 (Th11 = Cp*2Th(Cl)((Z)-3-imino- N1,N1,N2,N2-tetraisopropylbut-1-ene-1,2-diamine) and Th12 (Th12 = Cp*2Th(Cl)((Z)-3-imino-N1,N1,N2,N2-tetracyclohexylbut-1-ene-1,2-diamine). The ring-opening reaction is assisted by the nucleophilic attack of the thorium-coordinated methyl group to the highly strained cyclopropene imine carbon.

Norbornene Copolymerization with Polar Monomers Catalyzed by Palladium Catalysts Containing Imidazolidin-2-imine/Guanidine Ligands.

The development of a palladium catalyst that has enhanced catalytic performance, such as low aluminum cocatalyst loading, good copolymerization ability, high molecular weight, and excellent solubility of the (co)polymers, is still a challenge in norbornene copolymerizations. Here, a series of PdCl2 and PdMeCl complexes containing differently substituted anilines and imidazolidin-2-imine/guanidine ligands was successfully synthesized and characterized. X-ray diffraction analysis results revealed that these Pd complexes adopted an almost square-planar geometry, and the six-membered chelate ring showed structural distinctions as compared to traditional N^N-based α-diimine and ß-diimine Pd complexes. These Pd complexes were activated by EtAlCl2 and then exhibited moderate activity (104-105 g mol-1 h-1) and good thermal stability (up to 90 °C) for norbornene polymerization to produce high-molecular-weight PNBs (Mn up to 96.4 kg mol-1) with narrow polydispersities (PDI as low as 1.39). These Pd complexes also exhibited good polar group tolerance in the copolymerization of norbornene with methyl 5-norbornene-2-carboxylate and methyl 10-undecenoate, in which the activity was achieved up to 7.04 × 104 g mol-1 h-1. It furnished polar functionalized norbornene-based copolymers with high molecular weight (Mn up to 63.1 kg mol-1), narrow PDI, reasonable polar monomer incorporation, and good solubility. These Pd catalysts exhibited an enhanced copolymerization ability to produce PNB or NB-based copolymers, representing significant progress in this field.

An inexpensive paracetamol sensor based on an acid-activated carbon fiber microelectrode.

Paracetamol, a contaminant of emerging concern, has been detected in different bodies of water, where it can impact ecological and human health. To quantify this paracetamol, electroanalytical methods have gained support. Thus, the present study developed a simple, inexpensive, and environmentally friendly method for paracetamol quantification using a carbon fiber microelectrode based on commercial carbon fiber. To improve the carbon fiber microelectrode's paracetamol sensitivity and selectivity, it was subjected to an activation process via electrochemical oxidation in an acid medium (H2SO4 or HNO3), using 20 consecutive cycles of cyclic voltammetry. The treated (activated) carbon fiber microelectrode was characterized using scanning electron microscopy and electrochemical techniques, including chronoamperometry and electrochemical impedance spectroscopy. The H2SO4-activated carbon fiber microelectrode exhibited enhanced figures of merit, with a linear dynamic range of paracetamol detection from 0.5 to 11 µmol L-1 and a limit of detection of 0.21 µmol L-1 under optimized conditions. The method was optimized by quantifying paracetamol in commercial pharmaceutical tablets, spiked running tap water, and river water (Pita River, Quito, Ecuador, latitude -0.364955°, longitude -78.404538°); the respective recovery values were 102.89, 103.93, and 112.40%. The results demonstrated an acceptable level of accuracy and the promising applicability of this carbon fiber microelectrode as a sensor to detect paracetamol.

Catalytic regeneration of metal-hydrides from their corresponding metal-alkoxides via the hydroboration of carbonates to obtain methanol and diols.

Thorium complexes decorated with 5-, 6-, and 7-membered N-heterocyclic iminato ligands containing mesityl wingtip substitutions have been synthesized and fully characterized. These complexes were found to be efficient in the hydroboration of cyclic and linear organic carbonates with HBpin or 9-BBN promoting their decarbonylation and producing the corresponding boronated diols and methanol. In addition, the hydroboration of CO2 breaks the molecule into "CO" and "O" forming boronated methanol and pinBOBpin. Moreover, the demanding depolymerization of polycarbonates to the corresponding boronated diols and methanol opens the possibility of recycling polymers for energy sources. Increasing the core ring size of the ligands allows a better performance of the complexes. The reaction proceeds with high yields under mild reaction conditions, with low catalyst loading, and short reaction times, and shows a broad applicability scope. The reaction is achieved via the recycling of a high-energy Th-H moiety from a stable Th-OR motif. Experimental evidence and DFT calculations corroborate the formation of the thorium hydride species and the reduction of the carbonate with HBpin to the corresponding Bpin-protected alcohols and H3COBpin through the formate and acetal intermediates.

SNAP-Tag-Targeted MRI-Fluorescent Multimodal Probes.

Magnetic resonance imaging (MRI) is a powerful imaging modality, widely employed in research and clinical settings. However, MRI images suffer from low signals and a lack of target specificity. We aimed to develop a multimodal imaging probe to detect targeted cells by MRI and fluorescence microscopy. We synthesized a trifunctional imaging probe consisting of a SNAP-tag substrate for irreversible and specific labelling of cells, cyanine dyes for bright fluorescence, and a chelated GdIII molecule for enhancing MRI contrast. Our probes exhibit specific and efficient labelling of genetically defined cells (expressing SNAP-tag at their membrane), bright fluorescence and MRI signal. Our synthetic approach provides a versatile platform for the production of multimodal imaging probes, particularly for light microscopy and MRI.

Titanium complexes with unsymmetrically substituted imidazolin-2-iminato ligands.

The reaction of the unsymmetrical N-heterocyclic carbenes 1-(2,4,6-trimethylphenyl)-3-(adamantyl)imidazolin-2-ylidene (IAdMes, 1a) and 1-(2,6-diisopropylphenyl)-3-(adamantyl)imidazolin-2-ylidene (IAdDipp, 1b) with trimethylsilyl azide furnished the 2-(trimethylsilylimino)imidazolines 2a (ImAdMesNSiMe3) and 2b (ImAdDippNSiMe3). Desilylation by stirring in methanol gave the corresponding imidazolin-2-imines 3a (ImAdMesNH) and 3b (ImAdDippNH). 2a and 2b were treated with [TiCl4(THF)2] (THF = tetrahydrofuran) and [CpTiCl3] (Cp = η5-C5H5) to form the mono- and bis(imidazolin-2-iminato) titanium(IV) complexes [(ImAdRN)TiCl3] (4, R = Mes, Dipp), [Cp(ImAdRN)TiCl2] (5, R = Mes, Dipp), and [(ImAdRN)2TiCl2] (6, R = Mes, Dipp). The crystal structures of all compounds except 2b were determined by X-ray diffraction analysis.

A Sacrificial Iminato Ligand in the Catalytic Cyanosilylation of Ketones Promoted by Organoactinide Complexes.

Four new complexes containing the bis(pentamethylcyclopentadienyl)thorium(IV) moiety, Cp*2Th(L1)(Me) (Th2), Cp*2Th(L2)(Me) (Th3), Cp*2Th(L1)Cl (Th5), and Cp*2Th(L2)Cl (Th6), were synthesized in quantitative yields via the protonolysis reaction of the metallocene precursor complexes Cp*2Th(Me)2 (Th1) and Cp*2Th(Me)Cl (Th4) and the respective six- and seven-membered N-heterocyclic neutral imine ligands L1H and L2H. The molecular structures of all the complexes were established by single-crystal X-ray structure analyses. The synthesized complexes along with the precursor complexes were employed as catalysts for the cyanosilylation reaction of ketones with trimethylsilyl cyanide (Me3SiCN). The removal of the iminato ligand is necessary to trigger the reaction, allowing the formation of the active catalyst.

Remodeling of N-Heterocyclic Iminato Ligand Frameworks for the Facile Synthesis of Isoureas from Alcohols and Carbodiimides Promoted by Organoactinide (Th, U) Complexes.

A new class of actinide complexes [(L)An(N{SiMe3}2)3] (An = Th or U) (Th1-Th3 and U1-U3) supported by highly nucleophilic seven-membered N-heterocyclic iminato ligands were synthesized and fully characterized by single-crystal X-ray diffraction. These complexes were successfully exploited as powerful catalysts for the addition of alcohols to carbodiimides to yield the corresponding desirable isourea products at room temperature with short reaction times and excellent yields. Thorough stoichiometric, thermodynamic, and kinetic studies were carried out, allowing us to propose a plausible mechanism for the catalytic reaction.

Recent developments in highly basic N-heterocyclic iminato ligands in actinide chemistry.

In the last decade, major conceptual advances in the chemistry of actinide molecules and materials have been made to demonstrate their distinct reactivity profiles as compared to lanthanide and transition metal compounds, but some difficult questions remain concerning the intriguing stability of low-valent actinide complexes, and the importance of the 5f-orbitals in reactivity and bonding. The imidazolin-2-iminato moiety has been extensively used in ligands for the advancement of actinide chemistry owing to its unique capability of stabilizing the reactive and highly electrophilic metal ions by virtue of its strong electron donation and steric tunability. The current review article describes recent developments in the chemistry of light actinide metal ions (thorium and uranium) bearing these N-heterocyclic iminato moieties as supporting ligands. In addition, the effect of ring expansion of the N-heterocycle on the catalytic aptitude of the organoactinides is also described herein. The synthesis and reactivity of actinide complexes bearing N-heterocyclic iminato ligands are presented, and promising apposite applications are also presented. The current review focuses on addressing the catalytic behavior of actinide complexes with oxygen-containing substrates such as in the Tishchenko reaction, hydroelementation processes, and polymerization reactions. Actinide complexes have also found new catalytic applications, as demonstrated by the potent chemoselective carbonyl hydroboration and tandem proton-transfer esterification (TPTE) reaction, featuring coupling between an aldehyde and alcohol.

New Preparation Methods for Pore Formation on Polysulfone Membranes.

This work described the preparation of membranes based on aromatic polysulfones through the phase-inversion method induced by a nonsolvent, generating the phase separation (NIPS) process. Three new techniques, including the nano iron acid etching method, base hydrolysis method of crosslinked polymers, and base hydrolysis method of a reactive component in a binary polymer blend, were developed for pore creation on membranes. The modified polymers and obtained membranes were carefully characterized. The uniform pores were successfully created by base hydrolysis of the crosslinked polymers and obtained at the size of the crosslinker. Moreover, homogeneous pores were created after base hydrolysis of the membranes prepared from binary polymer blends due to the internal changes in the polymer structure. The separation performance of membranes was tested with different inorganic salt solutions and compared with commercially known membranes. These new membranes exhibited high water flux (up to 3000 L/m-2·h-1 at 10 bar and at 25 °C) and reasonable rejections for monovalent (21-44%) and multivalent ions (18-60%), depending on the different etching of the hydrolysis times. The comparison of these membranes with commercial ones confirmed their good separation performance and high potential application for water treatment applications.

Mild catalytic deoxygenation of amides promoted by thorium metallocene.

The organoactinide-catalyzed (Cp*2ThMe2) hydroborated reduction of a wide range of tertiary, secondary, and primary amides to the corresponding amines/amine-borane adducts via deoxygenation of the amides is reported herein. The catalytic reactions proceed under mild conditions with low catalyst loading and pinacolborane (HBpin) concentration in a selective fashion. Cp*2ThMe2 is capable of efficiently catalysing the gram-scale reaction without a drop in efficiency. The amine-borane adducts are successfully converted into free amine products in high conversions, which increases the usefulness of this catalytic system. A plausible mechanism is proposed based on detailed kinetics, stoichiometric, and deuterium labeling studies.

(Benz)Imidazolin-2-iminato Aluminum, Zinc, and Magnesium Complexes and Their Applications in Ring Opening Polymerization of ε-Caprolactone.

Synthesis and characterization of a new family of aluminum, magnesium, and zinc complexes supported by (benz)imidazolin-2-iminato ligands are reported herein. Under different reaction conditions, (benz)imidazolin-2-imine ligands reacted with metal alkyl precursors to afford the corresponding complexes, displaying mononuclear, binuclear, and trinuclear structures. Reaction in 1:1 stoichiometry at room temperature afforded the simple Lewis acid-base adducts, which exhibited distorted tetrahedral geometries around the metal centers, whereas high temperature reactions gave rise to dimeric complexes, with each metal bridging two (benz)imidazolin-2-imine ligands to form a four-membered metallacycle ring at the center of the complexes. The catalytic ring opening polymerization (ROP) of ε-caprolactone was studied using these complexes as precatalysts in the presence of isopropanol, and very high activities were observed, affording high/medium molecular weight poly(ε-caprolactone) products with low polydispersity indices. Detailed kinetic studies revealed that the polymerizations proceeded in a living manner and molecular weights of the polymers could be precisely controlled.

Catalytic regeneration of a Th-H bond from a Th-O bond through a mild and chemoselective carbonyl hydroboration.

Here we present an unprecedented chemoselective hydroboration for aldehydes and ketones catalysed by actinides. The reaction features a very low catalyst loading (0.1-0.004 mol%) and quantitative product formation in less than 15 minutes, at room temperature. Thermodynamic and kinetic studies including stoichiometric and labeling studies with deuterated pinacolborane allow us to propose a plausible mechanism for this remarkable catalytic regeneration of a Th-H bond via carbonyl hydroboration.

Organoactinide-Catalyzed Monohydroboration of Carbodiimides.

The organoactinide-catalyzed monohydroboration of carbodiimides is reported herein. The catalytic reactions proceed under very mild conditions in a highly atom-efficient and highly selective fashion to afford the corresponding monohydroborated N-borylformamidine products in high yields. A plausible mechanism is proposed based on stoichiometric and kinetic studies.

Organoactinides in catalytic transformations: scope, mechanisms and Quo Vadis.

The last decade has witnessed wonderful and remarkable advances in the chemistry of early actinides, providing information on not only the reactivity of these types of compounds in stoichiometric reactions but also their utilization in challenging catalytic processes. This canvas of knowledge allows the design of chemical reactivities to reach a high level of sophistication. As compared to early/late transition metal and lanthanide complexes, the actinides display complementary and in some cases real unique performances for similar organic transformations. The study of organoactinides allows us to design new chemical transformations due to their distinctive electronic structures, which feature a large coordination number exhibiting steric interactions. This review highlights the latest results obtained since 2008 on the catalytic activities of organoactinides. This review presents a brief introduction, and two main parts: (i) organoactinide mediated catalytic transformations of small molecules, including hydroelementation, coupling reactions, etc.; (ii) organoactinide catalysed polymerization and oligomerization reactions, including olefin, diene, cyclic ester and epoxide substrates. At the end, we present our Quo Vadis opinion and pose some challenging questions and our personal opinion regarding where this field should continue to develop.

Thorium complexes possessing expanded ring N-heterocyclic iminato ligands: synthesis and applications.

Six and seven membered N-heterocyclic iminato ligands (L) are introduced allowing access a new class of Th(iv) complexes of the type Cp*2Th(L)(CH3). These complexes were studied in the Tishchenko reaction. Stoichiometric reactions together with kinetic and thermodynamic studies permit us to propose a plausible mechanism.

Catalytic Addition of Alcohols into Carbodiimides Promoted by Organoactinide Complexes.

The insertion of alcohols into carbodiimides mediated by benzimidazolin-2-iminato actinide complexes [(BimR1/R2N)AnN″3] [N″ = N(SiMe3)2] is presented herein. Analysis of single-crystal data revealed that steric hindrance, rather than electronic properties, plays an important role in determining the accessibility for this insertion process. All actinide complexes showed excellent activities under very mild conditions. Stoichiometric reactions in combination with kinetic and thermodynamic studies allow us to propose a plausible active species and a mechanism for the catalytic cycle.

Synthesis of Coordinatively Unsaturated Tetravalent Actinide Complexes with η(5) Coordination of Pyrrole.

The synthesis of new actinide complexes utilizing bridged α-alkyl-pyrrolyl ligands is presented. Lithiation of the ligands followed by treatment with 1 equiv of actinide tetrachloride (uranium or thorium) produces the desired complex in good yield. X-ray diffraction studies reveal unique η(5):η(5) coordination of the pyrrolyl moieties; when the nonsterically demanding methylated ligand is used, rapid addition of the lithiated ligand solution to the metal precursor forms a bis-ligated complex that reveals η(5):η(1) coordination as determined by crystallographic analysis.

Actinide-Catalyzed Intermolecular Addition of Alcohols to Carbodiimides.

The unprecedented actinide-catalyzed addition of alcohols to carbodiimides is presented. This represents a rare example of thorium-catalyzed transformations of an alcoholic substrate and the first example of uranium complexes showing catalytic reactivity with alcohols. Using the uranium and thorium amides U[N(SiMe3)2]3 and [(Me3Si)2N]2An[κ(2)-(N,C)-CH2Si(CH3)2N(SiMe3)] (An = Th or U), alcohol additions to unsaturated carbon-nitrogen bonds are achieved in short reaction times with excellent selectivities and high to excellent yields. Computational studies, supported by experimental thermodynamic data, suggest plausible models of the profile of the reaction which allow the system to overcome the high barrier of scission of the actinide-oxygen bond. Accompanied by experimentally determined kinetic parameters, a plausible mechanism is proposed for the catalytic cycle.