ABSTRACT
The geminal Lewis pair (F5C2)2SbCH2P(tBu)2 (1) was prepared by reacting (F5C2)2SbCl with LiCH2P(tBu)2. Despite its extremely electronegative pentafluoroethyl substituents, the neutral 1 exhibits a relatively soft acidic antimony function according to the HSAB concept (hard-soft acid-base). These properties lead to a reversibility in the binding of CS2 to 1, as observed by VT-NMR spectroscopy, while no reaction with CO2 is observed. The reaction behaviour towards heterocumulenes and the specific interaction situation in the CS2 adduct were analysed by quantum chemical calculations. The FLP-type reactivity of 1 has also been demonstrated by reaction with a variety of small molecules (SO2, PhNCO, PhNCS, (MePh2P)AuCl). The reactions of 1 with PhNCO and PhNCS led to different types of cyclic addition products: PhNCO adds with its N[double bond, length as m-dash]C bond and PhNCS adds preferentially with its C[double bond, length as m-dash]S bond. The reaction of 1 with (MePh2P)AuCl gave an adduct {[(F5C2)2SbCH2(tBu)2P]2Au}+ with a clamp-like structure binding a chloride anion by its two antimony atoms in chelate mode. Compound 1 and its adducts have been characterised by X-ray diffraction experiments, multinuclear NMR spectroscopy, elemental analyses and computational calculations (DFT, QTAIM, IQA).
ABSTRACT
Diradicals based on a meta-quinodimethane (m-QDM) scaffold generally have a triplet ground state and are rather scarce. Herein, m-QDM-based non-Kekulé diradicals [3,3'-(NHC)2BP] (3-NHC) (NHC = SIPr = C{N(Dipp)CH2}2; IPr = C{N(Dipp)CH}2, Me-IPr = C{N(Dipp)CMe}2; Dipp = 2,6-iPr2C6H3; BP = 1,1'-C6H3C6H3) featuring N-heterocyclic carbene (NHC) pendants are reported as crystalline solids. The EPR spectra of 3-NHC show both allowed (Dms = 1) and forbidden (Dms = 2; 'half-field') transitions characteristic for triplet diradicals. Variable temperature EPR studies however reveal a singlet ground state for 3-SIPr. Consistent with the EPR spectra, calculations predict a remarkably small (open-shell) singlet-triplet energy gap (ΔEST ≤ 0.26 kcal/mol) for the 3-NHC compounds. The calculated singlet diradical character for the ground states of the 3-NHC compounds amounts to ~99%.
ABSTRACT
Bidentate and tetradentate chalcogen bonding host systems with SeCF3 functions as σ-hole donors in close proximity at the alkyne functions of 1,8-diethynylanthracene and its syn-dimer were prepared in quantitative yield by tin-selenium exchange reactions of the corresponding trimethylstannyl precursors with ClSeCF3. The bidentate system shows chalcogen bonding interactions with THF, but does not bind halide ions. The tetradentate system cooperatively chelates chloride, bromide and iodide ions with its four CîC-SeCF3 units by rotating the four σ-holes towards the halide ion. The structures of these halide ion adducts were determined by X-ray diffraction. The hydrobromide and -iodide salts of the ethyl derivative of Schwesinger's phosphazene superbase served as halide salts with very weakly coordinating cations.
ABSTRACT
Although the adduct of aluminum trichloride with thionyl chloride has been reported, no thionyl chloride adduct of a main group element Lewis acid or organometallic compound has been structurally characterized. In this communication we present the synthesis and reactivity of the structurally ascertained adduct of thionyl chloride with tris(pentafluoroethyl)gallane as a representative of a main group element Lewis acid. Gallium and indium compounds with electron withdrawing groups, e.g. the pentafluoroethyl ligand, display versatile properties. While gallates and indates, [MR4]-, behave as weakly coordinating anions, neutral gallanes and indanes, MR3, are strong Lewis acids. Salts with the tetrakis(pentafluoroethyl)gallate and -indate, [M(C2F5)4]- (M=Ga, In), have recently been studied in detail. In contrast to this, work on the syntheses of the free Lewis superacids M(C2F5)3 (M= Ga, In) is scarce and underdeveloped. The hydrates [M(C2F5)3(OH2)2] proved to be suitable starting materials, particularly due to their thermal stability. Herein we report on synthesis and characterization of reactive adducts, [M(C2F5)3D], with the weak donor molecules (D) SOCl2 and Me3SiF. The effective Lewis acidities of Ga(C2F5)3 and In(C2F5)3 were experimentally deter-mined by the (modified) Gutmann-Beckett method and their catalytic potential is showcased.
ABSTRACT
Flexible poly-Lewis acids (PLA) based on the tribenzotriquinacene (TBTQ) scaffold have been synthesised. Hydrosilylation of 4b,8b,12b-triallyltribenzotriquinacene and subsequent exchange of the chlorine substituents with weaker coordinating triflate groups afforded a novel triple silyl-functionalised PLA. By regioselective hydroboration of triallyl-TBTQ with various organoboranes, PLAs with different Lewis acidities were obtained. The synthesised PLAs were combined with neutral bases in host-guest experiments. DOSY NMR spectroscopy was performed to elucidate the complexation process in solution. These experiments revealed a highly dynamic interaction between the boron-functionalised PLA and triazine. However, the addition of one equivalent of tris(dimethylphosphino(methyl))phenylsilane led to the formation of a 1 : 1 adduct, which was confirmed by diffusion experiments.
ABSTRACT
The reactions of the frustrated Lewis pair (F5C2)2SbCH2P(tBu)2 with oxygen, sulphur, selenium and tellurium led to the mono-oxidation products (F5C2)2SbCH2P(E)(tBu)2 (E = O, S, Se, Te). Further oxidation of these chalcogen adducts with tetrachloro-ortho-benzoquinone (o-chloranil) gave (F5C2)2Sb(CH2)(µ-E)P(tBu)2·CatCl (CatCl = o-O2C6Cl4) with a central four-membered ring heterocycle for E = O, S, and Se. For E = Te the elimination of elemental tellurium led to an oxidation product with two equivalents of o-chloranil, (F5C2)2SbCH2P(tBu)2·2CatCl, which is also accessible by reaction of (F5C2)2SbCH2P(tBu)2 with o-chloranil. The synthesised compounds were characterised by NMR spectroscopy and X-ray structure analyses, and the structural properties were analysed in the light of the altered Lewis acidity due to the oxidation of the antimony atoms.
ABSTRACT
Chalice-shaped tridentate poly-Lewis acids (PLA) based on the tribenzotriquinacene (TBTQ) scaffold have been synthesised. Stannylation of the alkyne units, attached via phenyl-spacers to the benzhydrylic positions to the TBTQ scaffold, with Me2NSnMe3 afforded the trimethyltin substituted TBTQ derivative. Replacement of these tin functions with other elements resulted in rigid boron- and aluminium-functionalised PLAs. More flexible PLAs were obtained by hydrometallation reactions of the terminal alkyne groups of 4b,8b,12b-tris((ethynyl)phenyl)tribenzotriquinacene. The resulting poly-Lewis acids were tested for their acceptor abilities in host-guest experiments with suitable bases. Preliminary tests with pyridine led to the synthesis of a large tridentate base with three pyridyl groups attached to a TBTQ backbone. Complexation of this Lewis base with the PLAs resulted in the formation of aggregates, which were studied in solution in more detail by 1H DOSY NMR experiments regarding their size. Further experiments were performed with the tridentate bases 1,4,7-trimethyl-1,4,7-triazacyclononane and tris((dimethylphosphino)methyl)phenylsilane.
ABSTRACT
Four bidentate boron Lewis acids based on the 1,8-diethynylanthracene backbone have been synthesized by a tin-boron exchange reaction with various chloroboranes, yielding the products in good to excellent yields. Complexation experiments of the host compounds with pyridine, pyrimidine and TMEDA demonstrated striking differences in terms of formation and solubility of the supramolecular adducts. The host-guest complexes were investigated by multinuclear NMR spectroscopy and structurally characterized by X-ray diffraction experiments, illustrating the adaptation of the host system upon adduct formation with different neutral guest molecules.
ABSTRACT
Hexadentate poly-Lewis acids (PLA) based on the bowl-shaped tribenzotriquinacene (TBTQ) have been synthesised. The introduction of three n-propyl groups into the benzhydrylic positions of the TBTQ backbone has significantly increased the solubility of the subsequently derived compounds. Semi-flexible PLAs containing boron and aluminium were obtained by hydrometallation of the corresponding 2,3,6,7,10,11-hexaalkynyl-TBTQ. Other rigid hexadentate PLAs were synthesised by stannylation of the corresponding alkyne units with Me3SnNMe2 followed by tin-element exchange reactions. The Lewis acidity of these PLAs was investigated in host-guest experiments with pyridine. Further experiments with bidentate bases showed correlations between their flexibility, their Lewis basicity and the complexation behaviour towards the synthesised PLAs. Addition of bis((dimethylphosphino)methyl)dimethylsilane (BisPhos) to solutions of the rigid alkynyl PLAs led to the formation of 3 : 1 adducts. Single crystal X-ray diffraction was used to further elucidate the host-guest connectivtiy. In addition, a sixfold pnictogen-bonding donor was synthesised by tin-antimony exchange.
ABSTRACT
N-Heterocyclic carbene (NHC) analogues of Wittig hydrocarbon, [(NHC)(Stil)(NHC)] (3a-c) (NHC = SIPr (1a) = C[N(Dipp)CH2]2, Dipp = 2,6-iPr2C6H3; IPr (1b) = C[N(Dipp)CH]2; Me-IPr (1c) = C[N(Dipp)CMe]2 and Stil = C6H4CHCHC6H4) have been reported as crystalline solids. 3a-c are prepared by two-electron reductions of the corresponding bis-1,3-imidazoli(ni)um bromides [(NHC)(Stil)NHC)](Br)2 (2a-c) with KC8 in >94 % yields. 2a-c are accessible by the nickel catalyzed direct C-C coupling of NHCs (1a-c) with (E)-4,4'-dibromostilbene. One-electron oxidation of 3a,b yields the corresponding radical cations [(NHC)(Stil)NHC)]B(C6F5)4 4a,b. All compounds have been characterized by UV-Vis/NMR/EPR spectroscopy as well as 2a, 3a, and 3b by single crystal X-ray diffraction. The electronic structures of representative systems have been analyzed by quantum chemical calculations.
ABSTRACT
Carbocyclic aluminium halides [(ADC)AlX2]2 (2-X) (X=F, Cl, and I) based on an anionic dicarbene (ADC=PhC{N(Dipp)C}2, Dipp = 2,6-iPr2C6H3) framework are prepared as crystalline solids by dehydrohalogenations of the alane [(ADC)AlH2]2 (1). KC8 reduction of 2-I affords the peri-annulated Al(III) compound [(ADCH)AlH]2 (4) (ADCH=PhC{N(Dipp)C2(DippH)N}, DippH=2-iPr,6-(Me2C)C6H3)) as a colorless crystalline solid in 76 % yield. The formation of 4 suggests intramolecular insertion of the putative bis-aluminylene species [(ADC)Al]2 (3) into the methine C-H bond of HCMe2 group. Calculations predict singlet ground state for 3, while the conversion of 3 into 4 is thermodynamically favored by 61â kcal/mol. Compounds 2-F, 2-Cl, 2-I, and 4 have been characterized by NMR spectroscopy and their solid-state molecular structures have been established by single crystal X-ray diffraction.
ABSTRACT
A bidentate boron Lewis acid based on 1,8-diethynylanthracene has been studied in detail with respect to its adduct formation with diamines and diphosphanes of different linker lengths between the donor functions. A clear correlation between the linker length of the bifunctional base and the formation of 1 : 1 adducts, 1 : 2 adducts or oligomers was found. The adducts were characterized in solution by NMR titration experiments and structurally by X-ray diffraction. In addition, adduct formation and competition experiments of the host system with ZR3 (Z=N, P; R=H, Me) demonstrated the generally higher stability of alkylphosphane adducts compared to alkylamine adducts with boron functions. The results provide a general insight into the adduct formation of bidentate Lewis acids with guests of different sizes as well as the differences in stability between borane-amine and borane-phosphane adducts.
ABSTRACT
Herein, reactivity studies of a cyclic bis-hydridostannylene [(ADC)SnH]2 (1-H2) (ADC=PhC{(NDipp)C}2; Dipp=2,6-iPr2C6H3) with various unsaturated organic substrates are reported. Reactions of terminal alkynes (RC≡CH) with 1-H2 afford mixed acetylide-vinyl-functionalized bis-stannylenes via dehydrogenation and hydrostannylation. Treatment of 1-H2 with PhC≡CCH3 gives a unique distannabarrelene via dehydrogenative C(sp3)-H stannylation and hydrostannylation of the C≡CCH3 moiety. 1-H2 undergoes dehydrogenative [2+2]-cycloaddition reactions with diphenylacetylene, azobenzene, acetone, benzophenone, and benzaldehyde to form the 1,4-distannabarrelene derivatives. The elimination of H2 in these reactions suggests the masked-diradical property of 1-H2. In fact, these [2+2]-cycloaddition products are also accessible on treatments of the Sn(I) diradicaloid [(ADC)Sn]2 (1) with appropriate reagents. All compounds have been characterized by multinuclear NMR spectroscopy and single crystal X-ray diffraction. Moreover, the catalytic activity of 1-H2 has been shown for the hydroboration of unsaturated substrates.
ABSTRACT
We report the room temperature dimerization of carbon monoxide mediated by C4/C5-vicinal anionic dicarbenes Li(ADC) (ADC = ArC{(Dipp)NC}2 ; Dipp = 2,6-iPr2 C6 H3 ; Ar = Ph, DMP (4-Me2 NC6 H4 ), Bp (4-PhC6 H4 )) to yield (E)-ethene-1,2-bis(olate) (i.e. - O-C=C-O- = COen ) bridged mesoionic carbene (iMIC) lithium compounds COen -[(iMIC)Li]2 (COen -[iMIC]2 = [ArC{(Dipp)NC}2 (CO)]2 ) in quantitative yields. COen -[(iMIC)Li]2 are highly colored stable solids, exhibit a strikingly small HOMO-LUMO energy gap, and readily undergo 2e-oxidations with selenium, CuCl (or CuCl2 ), and AgCl to afford the dinuclear compounds COon -[(iMIC)E]2 (E = Se, CuCl, AgCl) featuring a 1,2-dione bridged neutral bis-iMIC (i.e. COon -[iMIC]2 = [ArC{(Dipp)NC}2 (C=O)]2 ). COen -[(iMIC)Li]2 undergo redox-neutral salt metathesis reactions with LiAlH4 and (Et2 O)2 BeBr2 and afford COen -[(iMIC)AlH2 ]2 and COen -[(iMIC)BeBr]2 , in which the dianionic COen -moiety remains intact. All compounds have been characterized by NMR spectroscopy, mass spectrometry, and X-ray diffraction. Stereoelectronic properties of COon -[iMIC]2 are quantified by experimental and theoretical methods.
ABSTRACT
Herein, ring-opening of mesoionic carbenes (iMICs) (iMIC=[ArC{N(Dipp)}2 C(SiMe3 )C:) (Dipp=2,6-iPr2 C6 H3 , Ar=Ph, 4-Me2 NC6 H4 or 4-PhC6 H4 ) based on an 1,3-imidazole scaffold to yield N-ethynylformimidamide (eFIM) derivatives as crystalline solids (eFIM={(Dipp)N=C(Ar)N(Dipp)}C≡CSiMe3 ) is reported. eFIMs are thermally stable under inert gas atmosphere and show moderate air stability (t1/2= 3â h for Ar=Ph). eFIMs are excellent surrogates of iMICs, which generally have a limited shelf-life, and readily undergo ring-closing click reactions with a variety of main-group as well as transition metal Lewis acids to form hitherto challenging iMIC-compounds in good to excellent yields. In addition to the relevance of eFIMs in the synthesis of iMIC-compounds, quantification of the stereoelectronic properties of a representative iMIC (Ar=Ph) by experimental and theoretical methods suggests remarkably σ-donor property and steric profile of these new ligand sets.
ABSTRACT
Decarbonylation of a cyclic bis-phosphaethynolatostannylene [(ADC)Sn(PCO)]2 based on an anionic dicarbene framework (ADC = PhC{N(Dipp)C}2 ; Dipp = 2,6-iPr2 C6 H3 ) under UV light results in the formation of a Sn2 P2 cluster compound [(ADC)SnP]2 as a green crystalline solid. The electronic structure of [(ADC)SnP]2 is analyzed by quantum-chemical calculations. At room temperature, [(ADC)SnP]2 reversibly binds with CO2 and forms [(ADC)2 {SnOC(O)P}SnP]. [(ADC)SnP]2 enables catalytic hydroboration of CO2 and reacts with elemental selenium and Fe2 (CO)9 to afford [(ADC)2 {Sn(Se)P2 }SnSe] and [(ADC)Sn{Fe(CO)4 }P]2 , respectively. All compounds are characterized by multinuclear NMR spectroscopy and their solid-state molecular structures are determined by single-crystal X-ray diffraction.
ABSTRACT
A highly halide affine, tetradentate pnictogen-bonding host-system based on the syn-photodimer of 1,8-diethynylanthracene was synthesized by a selective tin-antimony exchange reaction. The host carries four C[triple bond, length as m-dash]C-Sb(C2F5)2 units and has been investigated regarding its ability to act as a Lewis acidic host component for the cooperative trapping of halide ions (F-, Cl-, Br-, I-). The chelating effect makes this host-system superior to its bidentate derivative in competition experiments. It represents a charge-reversed crown-4 and has the ability to dissolve otherwise poorly soluble salts like tetra-methyl-ammonium chloride. Its NMR-spectroscopic properties make it a potential probe for halide ions in solution. Insights into the structural properties of the halide adducts by X-ray diffraction and computational methods (DFT, QTAIM, IQA) reveal a complex interplay of attractive pnictogen bonding interactions and Coulomb repulsion.
ABSTRACT
A bidentate pnictogen bonding host-system based on 1,8-diethynylanthracene was synthesized by a selective tin-antimony exchange reaction and investigated regarding its ability to act as a Lewis acidic host component for the complexation of Lewis basic or anionic guests. In this work, the novel C≡C-Sb(C2 F5 )2 unit was established to study the potential of antimony(III) sites as representatives for the scarcely explored pnictogen bonding donors. The capability of this partly fluorinated host system was investigated towards halide anions (Cl- , Br- , I- ), dimethyl chalcogenides Me2 Y (Y=O, S, Se, Te), and nitrogen heterocycles (pyridine, pyrimidine). Insights into the adduct formation behavior as well as the bonding situation of such Eâ â â Sb-CF moieties were obtained in solution by means of NMR spectroscopy, in the solid state by X-ray diffraction, by elemental analyses, and by computational methods (DFT, QTAIM, IQA), respectively.
ABSTRACT
Cyclic organoalane compounds [(ADCAr )AlH2 ]2 (ADCAr = ArC{(DippN)C}2 ; Dipp = 2,6-iPr2 C6 H3 ; Ar = Ph or 4-PhC6 H4 (Bp)) based on anionic dicarbene (ADC) frameworks have been reported as crystalline solids. Treatments of Li(ADCAr ) with LiAlH4 at room temperature afford [(ADCAr )AlH2 ]2 with the concomitant release of LiH. Compounds [(ADCAr )AlH2 ]2 are stable crystalline solids and are freely soluble in common organic solvents. They are annulated tricyclic compounds with an almost planar central C4 Al2 -core embedded between two peripheral 1,3-imidazole (C3 N2 ) rings. At room temperature, [(ADCPh )AlH2 ]2 readily reacts with CO2 to form two- and four-fold hydroalumination products [(ADCPh )AlH(OCHO)]2 and [(ADCPh )Al(OCHO)2 ]2 , respectively. Further hydroalumination reactivity of [(ADCPh )AlH2 ]2 has been shown with isocyanate (RNCO) and isothiocyanate (RNCS) species (R=alkyl or aryl group). All compounds have been characterized by NMR spectroscopy, mass spectrometry, and single-crystal X-ray diffraction.
ABSTRACT
The phytochemical investigation of the MeOH and CH2Cl2-MeOH (1:1) extracts from the flowers and twigs of Helichrysumfoetidum (L.) Moench (Asteraceae), which showed antileishmanial and antiplasmodial activities during the preliminary screening, led to the isolation of four undescribed compounds, including two ent-beyer-15-ene-type diterpenoids, foetidumins A (1) and B (2), one flavonoid, foetidumin C (3) and one chalcopyrone, foetidumin D (4). Additionally, fourteen known compounds comprising, two ent-beyer-15-ene-type diterpenoids (5-6), six flavonoids (7-12), two steroids (13-14), three triterpenoids (15-17), and one glyceryl monostearate (18) were also isolated. The chemical structures of foetidumins A-D were fully elucidated by analyses of their spectroscopic data. The structure and the stereochemistry of foetidumin A (1) were confirmed by SC-XRD analyses. Among the tested compounds, foetidumin C (3), erythroxylol A (6), and kaempferol (7) displayed the highest antileishmanial potency with IC50 values of 13.0, 11.8, and 11.1 µM, respectively. Foetidumin C (3) had no cytotoxicity toward Vero cells with the selectivity index > 3.59. Meanwhile, extracts of flowers and twigs had higher activity against Plasmodium falciparum chloroquine-sensitive (Pf3D7) strain with IC50 values of 3.66 and 10.52 µg/mL, respectively.