Stable Mesoionic N‐Heterocyclic Olefins (mNHOs)

We report a new class of stable mesoionic N‐heterocyclic olefins, featuring a highly polarized (strongly ylidic) double bond. The ground‐state structure cannot be described through an uncharged mesomeric Lewis‐structure, thereby structurally distinguishing them from traditional N‐heterocyclic olefins (NHOs). mNHOs can easily be obtained through deprotonation of the corresponding methylated N,N′‐diaryl‐1,2,3‐triazolium and N,N′‐diaryl‐imidazolium salts, respectively. In their reactivity, they represent strong σ‐donor ligands as shown by their coordination complexes of rhodium and boron. Their calculated proton affinities, their experimentally derived basicities (competition experiments), as well as donor abilities (Tolman electronic parameter; TEP) exceed the so far reported class of NHOs.     

N-Heterocyclic Olefin-Ligated Palladium(II) Complexes as Pre-Catalysts for Buchwald–Hartwig Aminations

New N-heterocyclic olefins (NHOs) are described with functionalization on the ligand heterocyclic backbone and terminal alkylidene positions. Various Pd^II–NHO complexes have been formed and their use as pre-catalysts in Buchwald–Hartwig aminations was explored. The most active system for catalytic C−N bond formation between hindered arylamine and arylhalide substrates was accessed by combining a backbone methylated NHO with [Pd(cinnamyl)Cl]₂ in the presence of NaOtBu as a base. In these active systems evidence suggests that catalysis is mediated by colloidal palladium metal, highlighting a different coordination ability of NHOs in comparison with commonly used N-heterocyclic carbene co-ligands.     

N‐Heterocyclic Olefins as Organocatalysts for Polymerization: Preparation of Well‐Defined Poly(propylene oxide)

The metal‐free polymerization of propylene oxide (PO) using a special class of alkene—N‐heterocyclic olefins (NHOs)—as catalysts is described. Manipulation of the chemical structure of the NHO organocatalyst allows for the preparation of the poly(propylene oxide) in high yields with high turnover (TON>2000), which renders this the most active metal‐free system for the polymerization of PO reported to date. The resulting polyether displays predictable end groups, molar mass, and a low dispersity (?_M<1.09). NHOs with an unsaturated backbone are essential for polymerization to occur, while substitution at the exocyclic carbon atom has an impact on the reaction pathway and ensures the suppression of side reactions.     

N-Heterocyclic Olefins as Electron Donors in Combination with Triarylborane Acceptors: Synthesis,Optical and Electronic Properties of D–π–A Compounds

N-heterocyclic olefins (NHOs), relatives of N-heterocyclic carbenes (NHCs), exhibit high nucleophilicity and soft Lewis basic character. To investigate their π-electron donating ability, NHOs were attached to triarylborane π-acceptors (A) giving donor (D)–π–A compounds 1 – 3 . In addition, an enamine π-donor analogue ( 4 ) was synthesized for comparison. UV–visible absorption studies show a larger red shift for the NHO-containing boranes than for the enamine analogue, a relative of cyclic (alkyl)(amino) carbenes (CAACs). Solvent-dependent emission studies indicate that 1 – 4 have moderate intramolecular charge-transfer (ICT) behavior. Electrochemical investigations reveal that the NHO-containing boranes have extremely low reversible oxidation potentials (e.g., for 3 , =−0.40 V vs. ferrocene/ferrocenium, Fc/Fc⁺, in THF). Time-dependent (TD) DFT calculations show that the HOMOs of 1 – 3 are much more destabilized than that of the enamine-containing 4 , which confirms the stronger donating ability of NHOs.     

Nucleophilic Activation of Sulfur Hexafluoride by N-Heterocyclic Carbenes and N-Heterocyclic Olefins: A Computational Study

Sulfur hexafluoride (SF₆) is considered as a potent greenhouse gas, whose effective degradation is challenging. Here we report a computational study on the nucleophilic activation of sulfur hexafluoride by N-heterocyclic carbenes and N-heterocyclic olefins. The result shows that the activation of SF₆ is both thermodynamically and kinetically favorable at mild condition using NHOs with fluoro-substituted azolium and sulfur pentafluoride anion being formed. The Gibbs free energy barrier during the activation of SF₆ has a linear relationship with the energy of HOMO of substrates, which could be a guideline for applying those compounds that feature higher energy in HOMO to activate SF₆ in high efficiency.     

Buchwald-Hartwig Amination of Coordinating Heterocycles Enabled by Large-but-Flexible Pd-BIAN-NHC Catalysts**

A new class of large-but-flexible Pd-BIAN-NHC catalysts (BIAN=acenaphthoimidazolylidene, NHC=N-heterocyclic carbene) has been rationally designed to enable the challenging Buchwald-Hartwig amination of coordinating heterocycles. This robust class of BIAN-NHC catalysts permits cross-coupling under practical aerobic conditions of a variety of heterocycles with aryl, alkyl, and heteroarylamines, including historically challenging oxazoles and thiazoles as well as electron-deficient heterocycles containing multiple heteroatoms with BIAN-INon (N,N′-bis(2,6-di(4-heptyl)phenyl)-7H-acenaphtho[1,2-d]imidazol-8-ylidene) as the most effective ligand. Studies on the ligand structure and electronic properties of the carbene center are reported. The study should facilitate the discovery of even more active catalyst systems based on the unique BIAN-NHC scaffold.     

Influence of a Pre-organized N-Donor Group on the Coordination of Trivalent Actinides and Lanthanides by an Aminopolycarboxylate Complexant

The thermodynamic influence of a pre-organized N-donor group on the coordination of trivalent actinides and lanthanides by an aqueous aminopolycarboxylate complexant has been investigated. The synthesized reagent, N-2-methylpicolinate-ethylenediamine-N,N′,N′-triacetic acid (EDTA-Mpic), resembles ethylenediamine-N,N,N′,N′-tetraacetic acid (EDTA) with a single acetate pendant arm replaced by a 6-carboxypyridin-2-ylmethyl group. The rigid N-donor picolinate functionality has a profound impact on ligand protonation and trivalent f element complexation equilibria, as demonstrated by potentiometric, spectroscopic, and liquid/liquid metal-partitioning studies as well as by molecular dynamics calculations. Relative to diethylenetriamine-N,N,N′,N′′,N′′-pentaacetic acid (DTPA), the ability to preferentially bind trivalent actinides over trivalent lanthanides was moderately lowered due to the presence of the N-(6-carboxypyridin-2-ylmethyl) substituent. The structural modification substantially amplifies the total ligand acidity of EDTA-Mpic. As a result the complexant sustains the metal complexation and efficient An³⁺/Ln³⁺ differentiation in aqueous mixtures of unprecedented acidity for this class of reagents.     

Organocatalytic Enantioselective Synthesis of Axially Chiral N,N′-Bisindoles

This study establishes the first organocatalytic enantioselective synthesis of axially chiral N,N′-bisindoles via chiral phosphoric acid-catalyzed formal (3+2) cycloadditions of indole-based enaminones as novel platform molecules with 2,3-diketoesters, where de novo indole-ring formation is involved. Using this new strategy, various axially chiral N,N′-bisindoles were synthesized in good yields and with excellent enantioselectivities (up to 87 % yield and 96 % ee). More importantly, this class of axially chiral N,N′-bisindoles exhibited some degree of cytotoxicity toward cancer cells and was derived into axially chiral phosphine ligands with high catalytic activity. This study provides a new strategy for enantioselective synthesis of axially chiral N,N′-bisindoles using asymmetric organocatalysis and is the first to realize the applications of such scaffolds in medicinal chemistry and asymmetric catalysis.     

The effect of ammonium polyphosphate on the mechanism of thermal degradation of polyureas

The thermal decomposition of structurally related N–H and N,N′-disubstituted polyureas (Table I) and their mixtures with ammonium polyphosphate (APP) was investigated by thermogravimetry (TG) and direct pyrolysis in a mass spectrometer (MS). The N–H polyureas (IV–VI) undergo a quantitative depolymerization process with the formation of oligomers with amine and isocyanate end groups. In contrast, the thermal degradation of the N,N′-disubstituted polyureas (I–III) proceeds by a different mechanism as a function of their chemical structure. The addition of APP lowers the thermal stability of the N,N′-disubstituted polyureas, whereas that of the N–H polyureas is unaltered. However, our data show that APP does not change the nature of the pyrolytic products. The destabilizing effect of the additive can be attributed to the catalytic action of the acid species formed by its thermal decomposition.     

Mononuclear Formamidinate Complexes of Lithium and Sodium

Treatment of N,N′‐bis(aryl)formamidines (FXylH = N,N′‐bis(2,6‐dimethylphenyl)formamidine, FEtH = N,N′‐bis(2,6‐diethylphenyl)formamidine, FisoH = N,N′‐bis(2,6‐diisopropylphenyl)formamidine) with nBuLi in the presence of tmeda (= N,N,N′,N′‐tetramethylethylenediamine) led to deprotonation of the amidine affording [Li(FXyl)(tmeda)] ( 1 ), [Li(FEt)(tmeda)] ( 2 ) and [Li(Fiso)(tmeda)] ( 3 ) respectively. Similar treatment of FXylH and FisoH with [Na{N(SiMe₃)₂}] in THF and pmdeta (= N,N,N′,N″,N″‐pentamethyldiethylenetriamine) yielded [Na(FXyl)(pmdeta)] ( 4 ) and [Na(Fiso)(pmdeta)] ( 5 ). All complexes were characterised by spectroscopy (NMR and IR) and X‐ray crystallography. Due to the bulkiness of the formamidinate ligands and the multidentate nature of the supporting neutral amine ligands (tmeda and pmdeta), all compounds were mononuclear with η²‐chelating formamidinate ligands in the solid state.     

Gold(I) Complexes Stabilized by Nine- and Ten-Membered N-Heterocyclic Carbene Ligands

Nine- and ten-membered N-heterocyclic carbene (NHC) ligands have been developed and for the first time their gold(I) complexes were synthesized. The protonated NHC pro-ligands 2 a – h were prepared by the reaction of readily available N,N′-diarylformamidines with bis-electrophilic building blocks, followed by anion exchange. In situ deprotonation of the tetrafluoroborates 2 a – h with tBuOK in the presence of AuCl(SMe₂) provided fast access to NHC-gold(I) complexes 3 – 10 . These new NHC-gold(I) complexes show very good catalytic activity in a cycloisomerization reaction (0.1 mol % catalyst loading, up to 100 % conversion) and their solid-state structures reveal high steric hindrance around the metal atom (%V_bur up to 53.0) which is caused by their expanded-ring architecture.     

Self-Assembled Monolayers of N-Heterocyclic Olefins on Au(111)

Self-assembled monolayers (SAMs) of N-heterocyclic olefins (NHOs) have been prepared on Au(111) and their thermal stability, adsorption geometry, and molecular order were characterized by X-ray photoelectron spectroscopy, polarized X-ray absorption spectroscopy, scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. The strong σ-bond character of NHO anchoring to Au induced high geometrical flexibility that enabled a flat-lying adsorption geometry via coordination to a gold adatom. The flat-lying adsorption geometry was utilized to further increase the surface interaction of the NHO monolayer by backbone functionalization with methyl groups that induced high thermal stability and a large impact on work-function values, which outperformed that of N-heterocyclic carbenes. STM measurements, supported by DFT modeling, identified that the NHOs were self-assembled in dimers, trimers, and tetramers constructed of two, three, and four complexes of NHO−Au-adatom. This self-assembly pattern was correlated to strong NHO−Au interactions and steric hindrance between adsorbates, demonstrating the crucial influence of the carbon-metal σ-bond on monolayer properties.     

Structural Diversity in Alkali Metal and Alkali Metal Magnesiate Chemistry of the Bulky 2,6‐Diisopropyl‐N‐(trimethylsilyl)anilino Ligand

Bulky amido ligands are precious in s‐block chemistry, since they can implant complementary strong basic and weak nucleophilic properties within compounds. Recent work has shown the pivotal importance of the base structure with enhancement of basicity and extraordinary regioselectivities possible for cyclic alkali metal magnesiates containing mixed n‐butyl/amido ligand sets. This work advances alkali metal and alkali metal magnesiate chemistry of the bulky arylsilyl amido ligand [N(SiMe₃)(Dipp)]^? (Dipp=2,6‐iPr₂‐C₆H₃). Infinite chain structures of the parent sodium and potassium amides are disclosed, adding to the few known crystallographically characterised unsolvated s‐block metal amides. Solvation by N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine (PMDETA) or N,N,N′,N′‐tetramethylethylenediamine (TMEDA) gives molecular variants of the lithium and sodium amides; whereas for potassium, PMDETA gives a molecular structure, TMEDA affords a novel, hemi‐solvated infinite chain. Crystal structures of the first magnesiate examples of this amide in [MMg{N(SiMe₃)(Dipp)}₂(μ‐nBu)]_∞ (M=Na or K) are also revealed, though these breakdown to their homometallic components in donor solvents as revealed through NMR and DOSY studies.     

Rhodium complexes with a new chiral nitrogen‐containing BINOL‐based diphosphite or phosphonite ligand: synthesis and application to hydroformylation of styrene and/or hydrogenation of prochiral olefins

Two new cationic rhodium(I) complexes with a chiral nitrogen‐containing BINOL‐based diphosphite or phosphonite ligand have been synthesized. Chiral diphosphite was prepared by the reaction of N‐phenyldiethanolamine with two equivalents of [(R)‐(1,1′‐binaphthalene‐2,2′‐diyl)]chlorophosphite. In its rhodium complex the ligand is bound to the metal via both phosphorus atoms, and a Rh–N interaction is also possible. Synthesis of the chiral phosphonite was achieved by the reaction of 2‐(N,N‐dimethylaminophenyl)‐bis(diethylamino)phosphine with one equivalent of R‐BINOL. In its rhodium complex, the ligand is P,N‐bonded, forming a five‐membered chelate ring. The first complex was applied to hydroformylation of styrene and displayed high activity and chemo‐ and regioselectivity, but unfortunately no asymmetric induction was found. Both complexes were evaluated in the hydrogenation of prochiral olefins with moderate activities and low enantioselectivities. Copyright © 2005 John Wiley & Sons, Ltd.     

Topology Controlled All-(Meth)acrylic Thermoplastic Elastomers by Multi-Functional Lewis Pairs-Mediated Polymerization

It remains challenging to synthesize all-(meth)acrylic triblock thermoplastic elastomers (TPEs), due to the drastically different reactivities between the acrylates and methacrylates and inevitable occurrence of side reactions during polymerization of acrylates. By taking advantage of the easy structural modulation features of N-heterocyclic olefins (NHOs), we design and synthesize strong nucleophilic tetraphenylethylene-based NHOs varying in the number (i.e. mono-, dual- and tetra−) of initiating functional groups. Its combination with bulky organoaluminum [ⁱBuAl(BHT)₂] (BHT=bis(2,6-di-^tBu-4-methylphenoxy)) constructs Lewis pair (LP) to realize the living polymerization of both acrylates and methacrylates, furnishing polyacrylates with ultrahigh molecular weight (M_n up to 2174 kg ⋅ mol⁻¹) within 4 min. Moreover, these NHO-based LPs enable us to not only realize the control over the polymers’ topology (i.e. linear and star), but also achieve triblock star copolymers in one-step manner. Mechanical studies reveal that the star triblock TPEs exhibit better mechanical properties (elongation at break up to 1863 % and tensile strength up to 19.1 MPa) in comparison with the linear analogs. Moreover, the presence of tetraphenylethylene group in the NHOs entitled the triblock TPEs with excellent AIE properties in both solution and solid state.     

One‐Pot Synthesis of Pyrimido[1,2‐a]benzimidazoles under Solvent‐Free Conditions

A series of pyrimido[1,2‐a]benzimidazoles were obtained from aldehydes, 2‐aminobenzimidazole and ethyl acetoacetate in good‐to‐excellent yields by a simple, mild, and efficient procedure utilizing N,N,N′,N′‐tetrabromobenzene‐1,3‐disulfonamide (TBBDA) and poly(N‐bromo‐N‐ethylbenzene‐1,3‐disulfonamide) (PBBS) as catalysts.     

Variation in coordination modes of aromatic N-oxides in lanthanum(III) coordination polymers

Two new coordination polymers of lanthanum(III) benzoate having pyridine N-oxide and 4,4′-bipyridyl-N,N′-dioxide as ancillary ligands are synthesized and characterized. Different binding modes of the N-oxide are demonstrated; pyridine N-oxide binds as a bridging ligand, whereas 4,4′-bipyridyl-N,N′-dioxide is monodentate.     

A one‐dimensional zinc(II) coordination polymer incorporating [1,1′‐biphenyl]‐4,4′‐dicarboxylate and N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide ligands

In the title compound, catena‐poly[[[N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide]chloridozinc(II)]‐μ‐[1,1′‐biphenyl]‐4,4′‐dicarboxylato‐[[N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide]chloridozinc(II)]‐μ‐[N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide]], [Zn₂(C₁₄H₈O₄)Cl₂(C₂₆H₂₂N₄O₂)₃]_n, the Zn^II centre is four‐coordinate and approximately tetrahedral, bonding to one carboxylate O atom from a bidentate bridging dianionic [1,1′‐biphenyl]‐4,4′‐dicarboxylate ligand, to two pyridine N atoms from two N,N′‐bis(pyridin‐3‐ylmethyl)‐[1,1′‐biphenyl]‐4,4′‐dicarboxamide ligands and to one chloride ligand. The pyridyl ligands exhibit bidentate bridging and monodentate terminal coordination modes. The bidentate bridging pyridyl ligand and the bridging [1,1′‐biphenyl]‐4,4′‐dicarboxylate ligand both lie on special positions, with inversion centres at the mid‐points of their central C—C bonds. These bridging groups link the Zn^II centres into a one‐dimensional tape structure that propagates along the crystallographic b direction. The tapes are interlinked into a two‐dimensional layer in the ab plane through N—H...O hydrogen bonds between the monodentate ligands. In addition, the thermal stability and solid‐state photoluminescence properties of the title compound are reported.     

1-Lithio-2,2-diphenyl-1-(phenylsulfonyl)ethen: Synthese und Kristallstruktur

Syntheses and Crystal Structure of 1-Lithio-2,2-diphenyl-1-(phenylsulfonyl)ethene Crystals of [1-lithio-2,2-diphenyl-1-(phenylsulfonyl)ethene]– N,N,N′,N′ -tetramethylethylenediamine (2/2) ( 2 ) were prepared by addition of BuLi to 1,1-diphenyl-2-(phenylsulfonyl)ethene ( 1 ) in the presence of N,N,N′,N′ -tetramethylethylenediamine (TMEDA) at low temperature. The X-ray structure analysis shows a centrosymmetric dimer bridged over an eight-membered (Li? O? S? O)₂ ring. There are no Li–C contacts to the C(α) atoms. Both Li cations are tetracoordinated via the sulfonyl O-atoms and the N-atoms of the TMEDA ligand. The X-ray structure analysis of 1,1-diphenyl-2-(phenylsulfonyl)ethene ( 1 ) also was determined to compare interatomic distances and angles.     

Acylation of Cellulose with N,N′‐Carbonyldiimidazole‐Activated Acids in the Novel Solvent Dimethyl Sulfoxide/Tetrabutylammonium Fluoride

Summary: Carboxylic acids were efficiently activated with N,N′‐carbonyldiimidazole (CDI) and applied for the acylation of cellulose under homogeneous conditions using dimethyl sulfoxide (DMSO)/tetrabutylammonium fluoride trihydrate (TBAF) as solvent. The simple and elegant method is a very mild and easily applicable tool for the synthesis of pure aliphatic, alicyclic, bulky, and unsaturated cellulose esters with degrees of substitution of up to 1.9. Products are soluble in organic solvents, e.g., DMSO or N,N‐dimethylformamide (DMF). The cellulose esters were characterized by elemental analysis, FT‐IR, ¹H and ¹³C NMR spectroscopy and show no impurities or substructures resulting from side reactions.

The esterification of cellulose using carboxylic acids activated in situ with N,N′‐carbonyldiimidazole.