Indium(III)-Catalyzed Haloalkynylation Reaction of Alkynes.

Green chemistry strives for sustainability at the molecular level and is gaining increasing relevance in the development of chemical reactions. The haloalkynylation reaction is a highly atom-economical C-C coupling reaction that was previously only achieved using transition metal catalysts. It enables the introduction of an alkyne unit and a halogen atom into the target molecule. Herein, we present a haloalkynylation reaction catalyzed by indium(III) halides. The use of indium(III) bromide as a catalyst leads exclusively to the cis addition products with yields up to 86 %. In addition, iodoacetylenes can be applied for the first time for the haloalkynylation reaction of internal alkynes which is an important step forward in the development of industrially relevant and sustainable catalysts. In contrast to gold catalysis, which proceeds via a similar mechanism, the use of alkyl-substituted haloacetylenes as reagents is also possible. Based on 13C labeling experiments and quantum chemical calculations, we postulate two possible mechanisms for the indium(III)-catalyzed haloalkynylation reactions.

From Neutral Diarsenes to Diarsene Radical Ions and Diarsene Dications.

Diarsene [L(MeO)GaAs]2 (L=HC[C(Me)N(Ar)]2, Ar=2,6-iPr2C6H3, 4) reacts with MeOTf and MeNHC (MeNHC=1,3,4,5-tetra-methylimidazol-2-ylidene) to the diarsene [L(TfO)GaAs]2 (5) and the carbene-coordinated diarsene [L(MeO)GaAsAs(MeNHC)Ga(OMe)L] (6). The NHC-coordination results in an inversion of the redox properties of the diarsene 4, which shows only a reversible reduction event at E1/2=-2.06 V vs Fc0/+1, whereas the carbene-coordinated diarsene 6 shows a reversible oxidation event at E1/2=-1.31 V vs Fc0/+1. Single electron transfer reactions of 4 and 6 yielded [K[2.2.2.]cryp][L(MeO)GaAs]2 (8) and [L(MeO)GaAsAs(MeNHC)-Ga(OMe)L][B(C6F5)4] (9) containing the radical anion [L(MeO)GaAs]2⋅- (8⋅-) and the NHC-coordinated radical cation [L(MeO)GaAsAs(MeNHC)Ga(OMe)L]⋅+ (9⋅+), respectively, while the salt-elimination reaction of the triflate-coordinated diarsene 5 with Na[B(C6F5)4] gave [LGaAs]2[B(C6F5)4]2 (11) containing the dication [LGaAs]2 2+ (112+). Compounds 1-11 were characterized by 1H and 13C NMR, EPR (8, 9), IR, and UV-Vis spectroscopy and by single crystal X-ray diffraction (sc-XRD). DFT calculations provided a detailed understanding of the electronic nature of the diarsenes (4, 6) and the radical ions (8⋅-, 9⋅+), respectively.

The Origin of Dual-Emission in PLICT Compounds - an Empirical Approach.

Fluorescence spectroscopy proves to be a powerful and versatile tool in scientific research, demanding ongoing advancements of fluorescence probes to cater to a broad range of applications. The particular interest lies in the development of fluorophores with multiplexing capability, emitting from more than one excited state depending on the polarity and viscosity of the surrounding medium. Here, we present a variety of novel dual planarized intramolecular charge transfer (PLICT) emitters based on cyano-1-aminoindole structures. We have chosen a combination of experimental studies, theoretical calculations and the creation of a unique fluorophore cataloging map. This map serves as a useful tool for empirically determining the origin of both fluorescence bands.

In situ Cyclization of Aromatic Thioethers in Emissive Materials to Generate Phosphorescent Dibenzothiophenes.

In this contribution, we explored the photocyclization of thioethers to highly substituted dibenzothiophenes (DBT) using solely UV-light without any need for additives. This cost-effective, robust and environmentally friendly approach yielded phosphorescent compounds, which were characterized through X-ray crystallography and state-of-the-art photophysical methods. The resulting DBTs feature ultralong photoluminescence lifetimes and quantum yields close to unity in frozen glassy matrices. The reaction mechanism was investigated in detail through a combination of quantum chemical calculations and experimental results, providing evidence that triplet states are involved in the cyclization process. Additionally, the photoreaction can also be induced within materials. For this purpose, the precursors can be integrated into polymer films or polymer resins suitable for 3D printing. Irradiation of these polymeric objects allows motifs with ultralong phosphorescence to be irreversibly inscribed through the proceeding photocyclization. The in situ photogeneration of DBTs from aromatic thioethers overcomes the observed incompatibilities regarding solubility in polymer resins for 3D printing.

Naphthalene Carboxylation in the Sulfate-Reducing Enrichment Culture N47 Is Proposed to Proceed via 1,3-Dipolar Cycloaddition to the Cofactor Prenylated Flavin Mononucleotide.

Polycyclic aromatic hydrocarbons are persistent pollutants of anthropogenic or natural origin in the environment and accumulate in anoxic habitats. In this study, we investigated the mechanism of the enzyme naphthalene carboxylase as a model reaction for polycyclic aromatic hydrocarbon activation by carboxylation. An enzyme assay was established with cell extracts of the highly enriched culture N47. In assays without addition of ATP, naphthalene carboxylase catalyzed a stable isotope exchange of the carboxyl group of naphthoate with 13C-labeled bicarbonate buffer, which can only occur via a partial backwards reaction of the naphthalene carboxylase reaction to an intermediate that does not include the carboxyl group. Hence, a new carboxyl group from the labeled bicarbonate is added upon forward reaction to the naphthoate. This indicates that the reaction mechanism consists of two or more steps and that at least the latter steps are reversible and ATP independent. Naphthalene carboxylation assays were carried out in deuterated buffer and revealed the incorporation of 0, 1, 2, or 3 deuterium atoms in the final product naphthoyl-coenzyme A, indicating that the reaction is fully reversible. Putative reaction mechanisms were tested by quantum mechanical calculations. The proposed mechanism of the reaction consists of three steps: the activation of the naphthalene by 1,3-dipolar cycloaddition of the cofactor prFMN to naphthalene, release of a proton and rearomatization producing a stable intermediate, and a carboxylation with a reverse 1,3-dipolar cycloaddition and cleavage of the bond to the cofactor producing 2-naphthoate. IMPORTANCE Pollution with polycyclic aromatic hydrocarbons poses a great hazard to humans and animals, with considerable long-term effects. The anaerobic degradation of polycyclic aromatic hydrocarbons in anoxic zones and anaerobic growth of such organisms is very slow, leading to only poor investigation of the degradation pathways, so far. In this work, we elucidated the mechanism of naphthalene carboxylase, a key enzyme in anaerobic naphthalene degradation. This is the first mechanism proposed for a carboxylase targeting nonsubstituted (polycyclic) aromatic compounds and can serve as a model for the initial activation reaction in the anaerobic degradation of benzene or nonsubstituted polycyclic aromatic hydrocarbons, as well as similar enzymatic reactions from the expanding class of UbiD-like (de)carboxylases.

Chalcogen-Bond-Induced Double Helix Based on Self-Assembly of a Small Planar Building Block.

As a rule, helical structures at the molecular level are formed by non-planar units. This makes the design of helices, starting from planar building blocks via self-assembly, even more fascinating. Until now, however, this has only been achieved in rare cases, where hydrogen and halogen bonds were involved. Here, we show that the carbonyl-tellurium interaction motif is suitable to assemble even small planar units into helical structures in solid phase. We found two different types of helices: both single and double helices, depending on the substitution pattern. In the double helix, the strands are connected by additional Te⋅⋅⋅Te chalcogen bonds. In the case of the single helix, a spontaneous enantiomeric resolution occurs in the crystal. This underlines the potential of the carbonyl-tellurium chalcogen bond to generate complex three-dimensional patterns.

Measurement of Nanometer Distances in Solution via 13 C NMR Spectroscopy-Shrinking of Macrocycles with Increasing Temperature.

For a molecular system, size and shape are of elementary importance for its function and properties. Therefore, the determination of distances within a molecule is essential. However, the commonly used methods are only suitable for distances smaller than 4 Šor larger than 15 Å. Here, we show that by incorporating a molecular spring, we can measure distances in macrocycles in the range of 10 Šusing 13 C NMR spectroscopy. The accuracy of the method also allows to determine the temperature dependence of the distances. In one case, we find a contraction of the length by almost 10 % upon heating. This shrinking due to heating can be considered as inverse thermoelasticity at the molecular level and is a previously completely overlooked phenomenon that can be used in the future as a tool to change the length and, thus, the function of a system.

C-H Activation of Unbiased C(sp3 )-H Bonds: Gold(I)-Catalyzed Cycloisomerization of 1-Bromoalkynes.

Selective functionalization of non-activated C(sp3 )-H bonds is a major challenge in chemistry, so functional groups are often used to enhance reactivity. Here, we present a gold(I)-catalyzed C(sp3 )-H activation of 1-bromoalkynes without any sort of electronic, or conformational bias. The reaction proceeds regiospecifically and stereospecifically to the corresponding bromocyclopentene derivatives. The latter can be readily modified, comprising an excellent library of diverse 3D scaffolds for medicinal chemistry. In addition, a mechanistic study has shown that the reaction proceeds via a so far unknown mechanism: a concerted [1,5]-H shift / C-C bond formation involving a gold-stabilized vinylcation-like transition state.

Syntheses and Structures of 5-Membered Heterocycles Featuring 1,2-Diphospha-1,3-Butadiene and Its Radical Anion.

LGa(P2 OC)cAAC 2 features a 1,2-diphospha-1,3-butadiene unit with a delocalized π-type HOMO and a π*-type LUMO according to DFT calculations. [LGa(P2 OC)cAAC][K(DB-18-c-6)] 3[K(DB-18-c-6] containing the 1,2-diphospha-1,3-butadiene radical anion 3⋅- was isolated from the reaction of 2 with KC8 and dibenzo-18-crown-6. 3 reacted with [Fc][B(C6 F5 )4 ] (Fc=ferrocenium) to 2 and with TEMPO to [L-H Ga(P2 OC)cAAC][K(DB-18-c-6)] 4[K(DB-18-c-6] containing the 1,2-diphospha-1,3-butadiene anion 4- . The solid state structures of 2, 3K(DB-18-c-6], and 4[K(DB-18-c-6] were determined by single crystal X-ray diffraction (sc-XRD).

Metal-Catalyzed Haloalkynylation Reactions.

Metal catalysis has revolutionized synthetic chemistry, leading to entirely new, very efficient transformations, which enable access to complex functionalized molecules. One such new transformation method is the haloalkynylation reaction, in which both a halogen atom and an alkynyl unit are transferred to an unsaturated carbon-carbon bond. This minireview summarizes the development of metal-catalyzed haloalkynylation reactions since their beginning about a decade ago. So far, arynes, alkenes and alkynes have been used as unsaturated systems and the reactivities of these systems are summarized in individual chapters of the minireview. Especially, the last few years have witnessed a rapid development due to gold-catalyzed reactions. Here, we discuss how the choice of the catalytic system influences the regio- and stereoselectivity of the addition.

Switching from Heteronuclear Allyl Cations to Vinyl Cations by Using a Chemical Charge Trap.

Halide abstraction of the carbene-coordinated pnictinidenes (MecAAC)EGa(Cl)L (E = As 1, Sb 2, Bi 3, MecAAC = [H2C(CMe2)2NDipp]C; L = HC[C(Me)NDipp]2; Dipp = 2,6-i-Pr2C6H3) yielded the series of cationic group 15 compounds [(MecAAC)EGaL][Al(ORF)4] (E = As 4, Sb 5; Al(ORF)4 = Al(OC(CF3)3)4) and [(MecAAC)EGaL][B(ArF)4] (E = Sb 6, Bi 7; B(ArF)4 = B[C6H3(CF3)2]4), which were characterized by heteronuclear NMR spectroscopy and sc-XRD. The electronic nature of the cations [(MecAAC)EGaL]+ is controlled by the central pnictogen atom, according to quantum chemical calculations. The calculations furthermore demonstrated that compounds containing the lighter pnictogens (E = N, P) are best described as heteronuclear allyl cations, whereas heavier pnictogen atoms (E = As, Sb, Bi) serve as a trap for the positive charge, resulting in carbene-stabilized heterovinyl-type structures.

Single-Electron Oxidation of Carbene-Coordinated Pnictinidenes-Entry into Heteroleptic Radical Cations and Metalloid Clusters.

Stable heavy main group element radicals are challenging synthetic targets. Although several strategies have been developed to stabilize such odd-electron species, the number of heavier pnictogen-centered radicals is limited. We report on a series of two-coordinated pnictogen-centered radical cations [(MecAAC)EGa(Cl)L][B(C6F5)4] (MecAAC = [H2C(CMe2)2NDipp]C; Dipp = 2,6-i-Pr2C6H3; E = As 1, Sb 2, Bi 3; L = HC[C(Me)NDipp]2) synthesized by one-electron oxidation of L(Cl)Ga-substituted pnictinidenes (MecAAC)EGa(Cl)L (E = As I, Sb II, Bi III). 1-3 were characterized by electron paramagnetic resonance (EPR) spectroscopy and single crystal X-ray diffraction (sc-XRD) (1, 2), while quantum chemical calculations support their description as carbene-coordinated pnictogen-centered radical cations. The low thermal stability of 3 enables access to metalloid bismuth clusters as shown by formation of [{LGa(Cl)}3Bi6][B(C6F5)4] (4).

Design of Azobenzene beyond Simple On-Off Behavior.

Azobenzenes are without a doubt the most widely used light-induced switching units, and there is a plethora of application examples ranging from supramolecular chemistry to material science and biological chemistry. Here, we present a smart azobenzene, in which the photoswitching capability of the azobenzene moiety can be reversibly switched on and off using a second unit (redox switch). This second switching unit is based on the variation of the strength of a chalcogen bond between the azo group and a Te-Ph unit in ortho position to the azo group. This allows the selective switching of only one azobenzene unit in the presence of other azobenzene switches. The entire double-switch is a very simple, small system that can also be easily synthesized. As a result, this double-switch can be used as a smarter replacement for the established azobenzene system in the future. For example, in contrast to the latter this double-switch could be employed to store state information analogous to a flip-flop in digital electronic systems.

Observation of Discrete Valence Tautomers in Crystalline Cyclopentadienyl Radicals.

Single crystal X-ray (sc XRD) analyses of three symmetrically substituted cyclopentadienyl radicals (1, 2, 5) containing sterically demanding aryl groups showed that they crystallize as discrete valence tautomers (Jahn-Teller distortion) in the solid state with the unpaired electron either located in the b1 orbital (type I, state 2B1), resulting in a localized radical with two adjacent double bonds, or the a2 orbital (type II, state 2A2), leading to an allyl-type radical. Their properties in solution were examined by EPR spectroscopy as well as cyclovoltammetry and UV/vis spectroscopy including two additional cyclopentadienyl radicals (1-5). The electronic nature of 1-5 was further investigated by quantum chemical calculations.

Synthesis and Reactivity of Heteroleptic Ga-P-C Allyl Cation Analogues.

Oxidative addition of cyclic alkyl(amino)carbene-coordinated phosphinidenes (Me cAAC)PX to LGa affords gallium-coordinated phosphinidenes LGa(X)-P(Me cAAC) (L=HC[C(Me)N(2,6-i-Pr2 C6 H3 )]2 ; X=Cl 1, Br 2), which react with NaBArF 4 and LiAl(ORF )4 to [LGaP(Me cAAC)][An] (An=B(C6 H3 (CF3 )2 )4 3, B(C6 F5 )4 4, Al(OC(CF3 )3 )4 5). The cations in 3-5 show substantial Ga-P double bond character and represent heteronuclear analogues of allyl cations according to quantum chemical calculations. The reaction of 4 with 4-dimethylaminopyridine (dmap) to adduct 6 confirms the strong electrophilic nature of the gallium center, whereas 5 reacts with ethyl isocyanate with C-C bond formation to the γ-C atom of the ß-diketiminate ligand and formation of compound 7.

Reversible and Irreversible [2+2] Cycloaddition Reactions of Heteroallenes to a Gallaphosphene.

[2+2] Cycloaddition reactions of gallaphosphene L(Cl)GaPGaL 1 (L=HC[C(Me)N(2,6-i-Pr2 C6 H3 )]2 ) with carbodiimides [C(NR)2 ; R=i-Pr, Cy] and isocyanates [RNCO; R=Et, i-Pr, Cy] yielded four-membered metallaheterocycles LGa(Cl)P[µ-C(X)NR]GaL (X=NR, R=i-Pr 2, Cy 3; X=O, R=Et 4, i-Pr 5, Cy 6). Compounds 4-6 reversibly react with CO2 via [2+2] cycloaddition at ambient temperature to the six-membered metallaheterocycles LGa(Cl)P[µ-C(O)O]-µ-C(O)N(R)GaL (R=Et 7, i-Pr 8, Cy 9). Compounds 2-9 were characterized by IR and heteronuclear (1 H, 13 C{1 H}, 31 P{1 H}) NMR spectroscopy and elemental analysis, while quantum chemical calculations provided a deeper understanding on the energetics of the reactions.

Multi-Talented Gallaphosphene for Ga-P-Ga Heteroallyl Cation Generation, CO2 Storage, and C(sp3 )-H Bond Activation.

Gallaphosphene L(Cl)GaPGaL (2; L=HC[C(Me)N(2,6-i-Pr2 C6 H3 )]2 ), which is synthesized by reaction of LGa(Cl)PCO (1) with LGa, reacts with [Na(OCP)(dioxane)2.5 ] to LGa(OCP)PGaL (3), whereas chloride abstraction with LiBArF 4 yields [LGaPGaL][BArF 4 ] (4; BArF 4 =B(C6 F5 )4 ). 4 represents a heteronuclear analog of the allyl cation according to quantum chemical calculations. Remarkably, 2 reversibly reacts with CO2 to yield L(Cl)Ga-P[µ-C(O)O]2 GaL (5), while reactions with acetophenone and acetone selectively give compounds 6 and 7 by C(sp3 )-H bond activation.

A Mechanistic Study on Reactions of Group 13 Diyls LM with Cp*SbX2 : From Stibanyl Radicals to Antimony Hydrides.

Oxidative addition of Cp*SbX2 (X=Cl, Br, I; Cp*=C5 Me5 ) to group 13 diyls LM (M=Al, Ga, In; L=HC[C(Me)N (Dip)]2 , Dip=2,6-iPr2 C6 H3 ) yields elemental antimony (M=Al) or the corresponding stibanylgallanes [L(X)Ga]Sb(X)Cp* (X=Br 1, I 2) and -indanes [L(X)In]Sb(X)Cp* (X=Cl 5, Br 6, I 7). 1 and 2 react with a second equivalent of LGa to eliminate decamethyl-1,1'-dihydrofulvalene (Cp*2 ) and form stibanyl radicals [L(X)Ga]2 Sb. (X=Br 3, I 4), whereas analogous reactions of 5 and 6 with LIn selectively yield stibanes [L(X)In]2 SbH (X=Cl 8, Br 9) by elimination of 1,2,3,4-tetramethylfulvene. The reactions are proposed to proceed via formation of [L(X)M]2 SbCp* as reaction intermediate, which is supported by the isolation of [L(Cl)Ga]2 SbCp (11, Cp=C5 H5 ). The reaction mechanism was further studied by computational calculations using two different models. The energy values for the Ga- and the In-substituted model systems showing methyl groups instead of the very bulky Dip units are very similar, and in both cases the same products are expected. Homolytic Sb-C bond cleavage yields van der Waals complexes from the as-formed radicals ([L(Cl)M]2 Sb. and Cp*. ), which can be stabilized by hydrogen atom abstraction to give the corresponding hydrides, whereas the direct formation of Sb hydrides starting from [L(Cl)M]2 SbCp* via concerted ß-H elimination is unlikely. The consideration of the bulky Dip units reveals that the amount of the steric overload in the intermediate I determines the product formation (radical vs. hydride).

From Noncovalent Chalcogen-Chalcogen Interactions to Supramolecular Aggregates: Experiments and Calculations.

This review considers noncovalent bonds between divalent chalcogen centers. In the first part we present X-ray data taken from the solid state structures of dimethyl- and diphenyl-dichalcogenides as well as oligoalkynes kept by alkyl-sulfur, -selenium, and -tellurium groups. Furthermore, we analyzed the solid state structures of medium sized (12-24 ring size) selenium coronands and medium to large rings with alkyne and alkene units between two chalcogen centers. The crystal structures of the cyclic structures revealed columnar stacks with close contacts between neighboring rings via noncovalent interactions between the chalcogen centers. To get larger space within the cavities, rings with diyne units between the chalcogen centers were used. These molecules showed channel-like structures in the solid state. The flexibility of the rings permits inclusion of guest molecules such as five-membered heterocycles and aromatic six-membered rings. In the second part we discuss the results of quantum chemical calculations. To treat properly the noncovalent bonding between chalcogens, we use diffuse augmented split valence basis sets in combination with electron correlation methods. Our model substances were 16 dimers consisting of two Me-X-Me (X = O, S, Se, Te) pairs and dimers of Me-X-Me/Me-X-CN (X = O, S, Se, Te) pairs. The calculations show the anticipated increase of the interaction energy from (Me-O-Me)2 (-2.15 kcal/mol) to (Me-O-Me/Me-Te-CN) (-6.59 kcal/mol). An analysis by the NBO method reveals that in the case of the chalcogen centers O and S the hydrogen bridges between the molecules dominate. However, in the case of Se and Te the major bonding between the pairs originates from dispersion forces between the chalcogen centers. It varies between -1.7 and -4.0 kcal/mol.

The Nature of Strong Chalcogen Bonds Involving Chalcogen-Containing Heterocycles.

Chalcogen bonds are σ hole interactions and have been used in recent years as an alternative to hydrogen bonds. In general, the electrostatic potential at the chalcogen atom and orbital delocalization effects are made responsible for the orientation of the chalcogen bond. Here, we were able to show by means of SAPT calculations that neither the induction (orbital delocalization effects) nor the electrostatic term is causing the spatial orientation of strong chalcogen bonds in tellurium-containing aromatics. Instead, steric interactions (Pauli repulsion) are responsible for the orientation. Against chemical intuition the dispersion energies of the examined tellurium-containing aromatics are far less important for the net attractive forces compared to the energies in the corresponding sulfur and selenium compounds. Our results underline the importance of often overlooked steric interactions (Pauli repulsion) in conformational control of σ hole interactions.