A bis(silylene)pyridine pincer ligand can stabilize mononuclear manganese(0) complexes: facile access to isolable analogues of the elusive d7-Mn(CO)5 radical.

Using the potentially tridentate N,N'-bis(N-heterocyclic silylene)pyridine [SiNSi] pincer-type ligand, 2,6-N,N'-diethyl-bis[N,N'-di-tert-butyl(phenylamidinato)silylene] diaminopyridine, led to the first isolable bis(silylene)pyridine-stabilized manganese(0) complex, {κ3-[SiNSi]Mn(dmpe)} 4 (dmpe = (Me2P)2C2H4), which represents an isolobal 17 VE analogue of the elusive Mn(CO)5 radical. The compound is accessible through the reductive dehalogenation of the corresponding dihalido (SiNSi)Mn(ii) complexes 1 (Cl) and 2 (Br) with potassium graphite. Exposing 4 towards the stronger π-acceptor ligands CO and 2,6-dimethylphenyl isocyanide afforded the related Mn(0) complexes κ2-[SiNSi]Mn(CO)3 (5) and κ3-[SiNSi]Mn(CNXylyl)2(κ1-dmpe) (6), respectively. Remarkably, the stabilization of Mn(0) in the coordination sphere of the [SiNSi] ligand favors the d7 low-spin electronic configuration, as suggested by EPR spectroscopy, SQUID measurements and DFT calculations. The suitability of 4 acting as a superior pre-catalyst in regioselective hydroboration of quinolines has also been demonstrated.

An Isolable 2,5-Disila-3,4-Diphosphapyrrole and a Conjugated Si=P-Si=P-Si=N Chain Through Degradation of White Phosphorus with a N,N-Bis(Silylenyl)Aniline.

White phosphorus (P4 ) undergoes degradation to P2 moieties if exposed to the new N,N-bis(silylenyl)aniline PhNSi2 1 (Si=Si[N(tBu)]2 CPh), furnishing the first isolable 2,5-disila-3,4-diphosphapyrrole 2 and the two novel functionalized Si=P doubly bonded compounds 3 and 4. The pathways for the transformation of the non-aromatic 2,5-disila-3,4-diphosphapyrrole PhNSi2 P2 2 into 3 and 4 could be uncovered. It became evident that 2 reacts readily with both reactants P4 and 1 to afford either the polycyclic Si=P-containing product [PhNSi2 P2 ]2 P2 3 or the unprecedented conjugated Si=P-Si=P-Si=NPh chain-containing compound 4, depending on the employed molar ratio of 1 and P4 as well as the reaction conditions. Compounds 3 and 4 can be converted into each other by reactions with 1 and P4 , respectively. All new compounds 1-4 were unequivocally characterized including by single-crystal X-ray diffraction analysis. In addition, the electronic structures of 2-4 were established by Density Functional Theory (DFT) calculations.

Predicting dinitrogen activation by borenium and borinium cations.

The activation of thermodynamically stable and kinetically inert dinitrogen (N2) has been a great challenge due to the significant strength of the triple bond. Recently, in an experimental study on N2 activation by boron species, a highly reactive two-coordinated borylene broke through the limitations of traditional strategies of N2 activation by metal species. Still, studies on metal-free N2 activation remain underdeveloped. Here, we systematically investigate a frustrated Lewis pair (FLP) combining carbene and borenium (or borinium) cations to screen potential candidates for N2 activation via density functional theory calculations. As a result, we found that two FLPs (closed form FLP, borenium and open form FLP, borinium) are able to activate N2 in a thermodynamically and kinetically favorable manner, with a low energy barrier of 9.6 and 7.3 kcal mol-1, respectively. Furthermore, aromaticity was found to play an important role in the stabilization of the products, supported by nucleus-independent chemical shift (NICS), anisotropy of the current-induced density (ACID) and electron density of delocalized bonds (EDDB) analysis. Our findings provide an alternative approach for metal-free N2 activation, highlighting the importance of FLP chemistry and aromaticity in N2 activation.

Phosphine-Stabilized Germylidenylpnictinidenes as Synthetic Equivalents of Heavier Nitrile and Isocyanide in Cycloaddition Reactions with Alkynes.

The reactions of chlorogermylene MsFluindtBu-GeCl 1, supported by a sterically encumbered hydrindacene ligand MsFluindtBu, with NaPCO(dioxane)2.5 and NaAsCO(18-c-6) in the presence of trimethylphosphine afforded trimethylphosphine-stabilized germylidenyl-phosphinidene 2 and -arsinidene 3, respectively. Structural and computational investigations reveal that the Ge-E' bond (E' = P and As) features a multiple-bond character. 2 and 3 exhibit diverse reactivity toward trimethylsilylacetylene and 4-tetrabutylphenylacetylene. Specifically, 2 underwent cycloadditions with both alkynes affording the first six-membered aromatic phosphagermabenzen-1-ylidenes 4 and 5, respectively, through the heavier isocyanide intermediate MsFluindtBu-PGe. In contrast, 3 could serve as a synthetic equivalent of heavier isocyanides and nitriles when treated with trimethylsilylacetylene and 4-tetrabutylphenylacetylene yielding arsagermene 6 and arsolylgermylene 7, respectively. The reaction mechanisms for the cycloadditions were investigated through density functional theory calculations. The reactivity studies highlight the potential of 2 and 3 in accessing heavy main-group element-containing heterocycles.

Predicting Dinitrogen Activation by Five-Electron Boron-Centered Radicals.

Due to the high bond dissociation energy (945 kJ mol-1) and the large highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap (10.8 eV), dinitrogen activation under mild conditions is extremely challenging. On the other hand, the conventional Haber-Bosch ammonia synthesis under harsh conditions consumes more than 1% of the world's annual energy supply. Thus, it is important and urgent to develop an alternative approach for dinitrogen activation under mild conditions. In comparison with transition metals, main group compounds are less explored for nitrogen activation. Here, we carry out density functional theory calculation to screen boron radicals for dinitrogen activation. As a result, the experimentally available seven-electron boron-centered radicals are found to be inactive to N2 activation, whereas some five-electron boron-centered radicals become favorable for dinitrogen activation, inviting experimental chemists' examination. The principal interacting spin-orbital analyses suggest that a five-electron boron-centered radical can mimic a transition metal on a synergic interaction with dinitrogen in the transition states.

A Genuine Stannylone with a Monoatomic Two-Coordinate Tin(0) Atom Supported by a Bis(silylene) Ligand.

The monoatomic zero-valent tin complex (stannylone) {[SiII (Xant)SiII ]Sn0 } 5 stabilized by a bis(silylene)xanthene ligand, [SiII (Xant)SiII =PhC(NtBu)2 Si(Xant)Si(NtBu)2 CPh], and its bis-tetracarbonyliron complex {[SiII (Xant)SiII ]Sn0 [Fe(CO)4 ]2 } 4 are reported. The stannylone 5 bearing a two-coordinate zero-valent tin atom is synthesized by reduction of the precursor 4 with potassium graphite. Compound 4 results from the SnII halide precursor {[SiII (Xant)SiII ]SnII Cl}Cl 2 or {[SiII (Xant)SiII ]SnBr2 } 3 through reductive salt-metathesis reaction with K2 Fe(CO)4 . According to density functional theory (DFT) calculations, the highest occupied molecular orbital (HOMO) and HOMO-1 of 5 correspond to a π-type lone pair with delocalization into both adjacent vacant orbitals of the SiII atoms and a σ-type lone pair at the Sn0 center, respectively, indicating genuine stannylone character.

A Conjugated Figure-of-Eight Oligoparaphenylene Nanohoop with Adaptive Cavities Derived from Cyclooctatetrathiophene Core.

A fully conjugated figure-of-eight nanohoop is presented with facile synthesis. The molecule's lemniscular skeleton features the combination of two strained oligoparaphenylene loops and a flexible cyclooctatetrathiophene core. Its rigid yet guest-adaptive cavities enable the formation of the peanut-like 1:2 host-guest complexes with C60 or C70 , which have been confirmed by X-ray crystallography and characterized in solution. Further computational studies suggest notable geometric variations and non-covalent interactions of the cavities upon binding with different fullerenes, as well as overall conjugation comparable to cycloparaphenylenes.

Adaptive σ-Aromaticity in an Unsaturated Three-Membered Ring.

Based on Hückel's and Baird's rules, species are aromatic either in the lowest singlet state (S0 ) or the lowest triplet state (T1 ) only. Thus, species with adaptive aromaticity (with aromaticity in both the S0 and T1 states) is particularly rare. On the other hand, σ-aromaticity in the T1 state has been underdeveloped, let alone adaptive σ-aromaticity. Herein, via various aromaticity indices including NICS, ACID and EDDB, we demonstrate adaptive σ-aromaticity in an unsaturated three-membered ring, which is a traditional area dominated by π-aromaticity. The origin of adaptive σ-aromaticity could be attributed to the excitation mode of the T1 state formed from out-of-plane π molecular orbital to the π* orbitals. Thus the σ-aromaticity of the three-membered ring in the S0 state could hold in the T1 state. Our findings extend the concept of adaptive σ-aromaticity into three-membered rings and could be useful to further develop the concept of both σ-aromaticity and adaptive aromaticity.

Screening Borane Species for Dinitrogen Activation.

Activation of the strongest triplet bond in molecular nitrogen (N2) under mild conditions is particularly challenging. Recently, its fixation and reduction were achieved by highly reactive dicoordinated borylene species at ambient conditions, ripping the limits of harsh reaction conditions by metallic species. Less reactive species with a facile preparation could be desirable for next-generation N2 activation. Now density functional theory calculations reveal that tricoordinated boranes could be a potential candidate of N2 activation/functionalization. As composites of an intramolecular frustrated Lewis pair (FLP), optimal and realistic boranes are screened out to activate N2 in a significantly favorable manner (both thermodynamically and kinetically). The significant thermodynamic stabilities of the FLP-N2 adducts as well as the low activation barriers could be particularly interesting for the development of borane-based FLP chemistry applied in N2 activation.

Achieving Adaptive Aromaticity in Cyclo[10]carbon by Screening Cyclo[n]carbon (n=8-24).

Discovery of species with adaptive aromaticity (being aromatic in both the lowest singlet and triplet states) is particularly challenging as cyclic species are generally aromatic either in the ground state or in the excited state only, according to Hückel's and Baird's rules. Inspired by the recent realization of cyclo[18]carbon, here we demonstrate that cyclo[10]carbon possesses adaptive aromaticity by screening cyclo[n]carbon (n=8-24), which is supported by nucleus-independent chemical shift (NICS), anisotropy of the current-induced density (ACID), π contribution of electron localization function (ELFπ ) and electron density of delocalized bonds (EDDB) analyses. Further study reveals that the lowest triplet state of cyclo[10]carbon is formed by in-plane ππ* excitation. Thus, the major contribution to the aromaticity from out-of-plane π molecular orbitals does not change significantly in the lowest singlet state. Our findings highlight a crucial role of out-of-plane π orbitals in maintaining aromaticity for both the lowest singlet and triplet states as well as the aromaticity dependence on the number of the carbon in cyclo[n]carbon.

Discovery of dihydropyrrolidones as novel inhibitors against influenza A virus.

More effective prophylactic and therapeutic strategies to combat influenza viruses are urgently required worldwide because the conventional anti-influenza drugs are facing drug resistance. Here, dihydropyrrolidones (DHPs), the products of an efficient multi-components reaction, were found to possess good activities against influenza A virus (IAV). Primary structure-activity relationship indicated that the activities of DHPs were greatly influenced by substituents and four of them had IC50 values lower than 10 µM (DHPs 5-2, 8, 14 and 19: IC50 = 3.11-9.23 µM). The activities against multiple IAV strains and mechanism of DHPs were further investigated by using 5-2 (IC50 = 3.11 µM). It was found that 5-2 possessed antiviral effects against all the investigated subtypes of IAVs with the IC50 values from 3.11 to 7.13 µM. Moreover, 5-2 showed very low cytotoxicity with CC50 > 400 µM. Results of mechanism study indicated that 5-2 could efficiently inhibit replication of IAV, up-regulate the expression of key antiviral cytokines IFN-ß and antiviral protein MxA, and suppress the production of the NDAPH oxidase NOX1 in MDCK cells. These results indicated that 5-2 could be used as a potential inhibitor against wide subtypes of IAVs.

Aromaticity-promoted CO2 Capture by P/N-Based Frustrated Lewis Pairs: A Theoretical Study.

Carbon dioxide (CO2 , a common combustion pollutant) releasing continuously into the atmosphere is primarily responsible for the rising atmospheric temperature. Therefore, CO2 sequestration has been an indispensable area of research for the past several decades. On the other hand, the concept of aromaticity is often employed in designing chemical reactions and metal-free frustrated Lewis pairs (FLPs) have proved ideal reagents to achieve CO2 reduction. However, considering FLP and aromaticity together is less developed in CO2 capture. Here we report theoretical investigations on the aromaticity-promoted CO2 activation, involving heterocyclopentadiene-bridged P/N-FLPs. The calculations reveal that furan- and pyrrole-bridged P/N-FLPs can make CO2 capture both thermodynamically and kinetically favorable (with activation energies of 5.4-7.7 kcal mol-1 ) due to the aromatic stabilization of the transition states and products. Our findings could open an avenue to the design of novel FLPs for CO2 capture.