Samarium(II) Monoalkyl Complex Supported by a β-Diketiminato-Based Tetradentate Ligand: Synthesis,Structure, and Catalytic Hydrosilylation of Internal Alkynes

The synthesis and catalytic applications of trivalent rare-earth metal alkyl complexes have been well developed, but the chemistry of divalent rare-earth metal alkyl complexes lagged much behind. Herein, we report the synthesis, structure, and catalytic applications of a samarium(II) monoalkyl complex supported by a β-diketiminato-based tetradentate ligand, [LSmCH(SiMe₃)₂] (L=[MeC(NDipp)CHC(Me)NCH₂CH₂N(Me)CH₂CH₂NMe₂]⁻, Dipp=2,6-(iPr)₂C₆H₃). This complex is synthesized by the salt metathesis reaction of samarium iodide [LSm(μ-I)]₂ and KCH(SiMe₃)₂ in 63 % yield. Its structure is characterized by single-crystal X-ray diffraction, showing a distorted square-pyramid coordination geometry. This samarium(II) monoalkyl complex exhibits high catalytic activity in the hydrosilylation of aryl and methyl-substituted unsymmetrical internal alkynes with secondary hydrosilanes, selectively providing the α-(E) products in high yields.     

Synthesis,Structure, Reactivity and Catalytic Implications of a Cationic,Acetylide-Bridged Trigold–JohnPhos Species

The cationic complex [(JohnPhos–Au)₃(acetylide)][SbF₆] (JohnPhos=(2-biphenyl)di-tert-butylphosphine, L1) has been characterised structurally and features an acetylide–trigold(I)–JohnPhos system; the trinuclear–acetylide unit, coordinated to the monodentate bulk phosphines, adopts an unprecedented μ,η¹,η²,η¹ coordination mode with an additional interaction between distal phenyl rings and gold centres. Other cationic σ,π-[(gold(I)L1)₂] complexes have also been isolated. The reaction of trimethylsilylacetylene with various alcohols (iPrOH, nBuOH, n-HexOH) catalysed by cationic [Au^IL1][SbF₆] complexes in CH₂Cl₂ at 50 °C led to the formation of acetaldehyde acetals with a high degree of chemo- and regioselectivity. The reaction mechanism was studied, and several organic and inorganic intermediates have been characterised. A comparative study with the analogous cationic [Cu^IL1][PF₆] complex revealed different behaviour; the copper metal is lost from the coordination sphere leading to the formation of cationic vinylphosphonium and copper nanoparticles. Additionally, a new catalytic approach for the formation of this high-value cationic vinylphosphonium has been established.     

Iridium-Catalyzed Regioselective B(3)-Alkenylation/B(3,6)-Dialkenylation of o-Carboranes by Direct B−H Activation

Iridium-catalyzed formal alkyne hydroboration with cage B−H of o-carborane has been achieved, leading to the controlled synthesis of a series of 3,6-[trans-(AlkCH=CH)]₂-o-carboranes (Alk=alkyl), 3-cis-(ArCH=CH)-o-carboranes (Ar=aryl), and 3-cis-(ArCH=CH)-6-trans-(AlkCH=CH)-o-carboranes in high yields with excellent regio- and very good cis–trans selectivity. The most electron-deficient B(3,6)−H vertices favor oxidative addition on electron-rich metal centers, which is responsible for the regioselectivity. On the other hand, the configuration of the resultant olefinic units is dominated by alkyne substituents. Alkyl groups lead to a trans-configuration whereas bulky aryl substitutions result in cis-configuration.     

Rhodium(III)-Catalyzed C−H/N−H Functionalization with Hydrogen Evolution

A rhodium(III)-catalyzed C−H/N−H bond functionalization of benzimidates with α-chloroaldehydes to afford isoquinolin-3-ol derivatives is reported. No external oxidants are needed in this process, and interestingly, evolution of hydrogen gas is observed.     

Metal-Free,Visible-Light-Induced Selective C−C Bond Cleavage of Cycloalkanones with Molecular Oxygen

A metal-free, visible-light-induced oxidative C−C bond cleavage of cycloketones with molecular oxygen is described. Cooperative Brønsted-acid catalysis and photocatalysis enabled selective C−C bond cleavage of cycloketones to generate an array of γ-, δ- and ϵ-keto esters under very mild conditions. Mechanistic studies indicate that singlet molecular oxygen (¹O₂) is responsible for this transformation.     

NIR Light-Induced ATRP for Synthesis of Block Copolymers Comprising UV-Absorbing Moieties

NIR exposure at 790 nm activated photopolymerization of monomers comprising UV-absorbing moieties by using [Cu^II/(TPMA)]Br₂ (TPMA=tris(2-pyridylmethyl)amine) in the ppm range and an alkyl bromide as initiator. Some of them comprised structural elements selected either from those showing proton transfer or photocycloaddition upon UV excitation. Polymers obtained comprise living end groups serving as macroinitiator for controlled synthesis of block copolymers with relatively narrow molecular weight distributions. Chromatographic results indicated formation of block copolymers produced by this synthetic approach. Free-radical polymerization of monomers pursued for comparison exhibited the expected broader dispersity of molecular weight compared to photo-ATRP. Polymerization of these monomers by UV photo-ATRP failed on the contrary to NIR photo-ATRP demonstrating the UV-filter function of the monomers. This work conclusively provides a new approach for the polymerization of monomers comprising UV-absorbing moieties through photo-ATRP in the NIR region. This occurred in a simple and efficient pathway. However, studies also showed that not all monomers chosen successfully proceeded in the NIR photo-ATRP protocol.     

Three-Component Reaction for the Synthesis of Highly Functionalized Propargyl Ethers

Multicomponent reactions provide efficient means to access molecular complexity. Herein, we report a copper-catalyzed three-component reaction of diazo compounds, alcohols and ethynyl benziodoxole (EBX) reagents for the synthesis of propargyl ethers. Extensive variations of the three partners of the reaction is possible, leading to highly functionalized and structurally diverse products under mild conditions. Alkynylation of a copper ylide intermediate is postulated as key step for this transformation.     

Enantioselective Synthesis of Polycyclic Aromatic Hydrocarbon (PAH)-Based Planar Chiral Bent Cyclophanes by Rhodium-Catalyzed [2+2+2] Cycloaddition

The enantioselective synthesis of polycyclic aromatic hydrocarbon (PAH)-based planar chiral cyclophanes was achieved for the first time by the rhodium-catalyzed intramolecular regio- and enantioselective [2+2+2] cycloaddition of tethered diyne-benzofulvenes followed by stepwise oxidative transformations. The thus synthesized planar chiral bent cyclophanes, that possess bent p-terphenyl- and 9-fluorenone-cores, were converted to 9-fluorenol-based ones with excellent ee values of >99 % by diastereoselective 1,2-reduction. These 9-fluorenol-based cyclophanes exhibited high fluorescence quantum yields, which were significantly higher than that of an acyclic reference molecule (78–82 % vs. 48 %). The bending effect on the chiroptical property was also examined, which revealed that the anisotropy factors (g_abs values) for electronic circular dichroism (ECD) of these 9-fluorenol-based planar chiral bent cyclophanes increase as the tether length becomes shorter.     

Hydrogen-Bond Catalysis of Imine Exchange in Dynamic Covalent Systems

The reversibility of imine bonds has been exploited to great effect in the field of dynamic covalent chemistry, with applications such as preparation of functional systems, dynamic materials, molecular machines, and covalent organic frameworks. However, acid catalysis is commonly needed for efficient equilibration of imine mixtures. Herein, it is demonstrated that hydrogen bond donors such as thioureas and squaramides can catalyze the equilibration of dynamic imine systems under unprecedentedly mild conditions. Catalysis occurs in a range of solvents and in the presence of many sensitive additives, showing moderate to good rate accelerations for both imine metathesis and transimination with amines, hydrazines, and hydroxylamines. Furthermore, the catalyst proved simple to immobilize, introducing both reusability and extended control of the equilibration process.     

Diazaphospholene and Diazaarsolene Derived Homogeneous Catalysis

The past 20 years has seen significant advances in main group chemistry and their use in catalysis. This Minireview showcases the recent emergence of phosphorus and arsenic containing heterocycles as catalysts. With that, we discuss how the Group 15 compounds diazaphospholenes, diazaarsolenes, and their cationic counterparts have proven to be highly effective catalysts for a wide range of reduction transformations. This Minireview highlights how the initial discovery by Gudat of the hydridic nature of the P−H bond in these systems led to these compounds being used as catalysts and discusses the wide range of examples currently present in the literature.