Access to a peri-Annulated Aluminium Compound via C-H Bond Activation by a Cyclic Bis-Aluminylene.

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 61 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.

Boosting the π-Acceptor Property of Mesoionic Carbenes by Carbonylation with Carbon Monoxide.

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.

Ring-Opening of 1,3-Imidazole Based Mesoionic Carbenes (iMICs) and Ring-Closing Clicks: Facile Access to iMIC-Compounds.

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= 3 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.

Highly Soluble Cyclic Organoalanes Based on Anionic Dicarbenes.

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.

Crystalline Anions Based on Classical N-Heterocyclic Carbenes.

Herein, the first stable anions K[SIPrBp ] (4 a-K) and K[IPrBp ] (4 b-K) (SIPrBp =BpC{N(Dipp)CH2 }2 , IPrBp =BpC{N(Dipp)CH}2 ; Bp=4-PhC6 H4 ; Dipp=2,6-iPr2 C6 H3 ) derived from classical N-heterocyclic carbenes (NHCs) (i.e. SIPr and IPr) have been isolated as violet crystalline solids. 4 a-K and 4 b-K are prepared by KC8 reduction of the neutral radicals [SIPrBp ] (3 a) and [IPrBp ] (3 b), respectively. The radicals 3 a and 3 b as well as [Me-IPrBp ] 3 c (Me-IPrBp =BpC{N(Dipp)CMe}2 ) are accessible as crystalline solids on treatment of the respective 1,3-imidazoli(ni)um bromides (SIPrBp )Br (2 a), (IPrBp )Br (2 b), and (Me-IPrBp )Br (2 c) with KC8 . The cyclic voltammograms of 2 a-2 c exhibit two one-electron reversible redox processes in -0.5 to -2.5 V region that correspond to the radicals 3 a-3 c and the anions (4 a-4 c)- . Computational calculations suggest a closed-shell singlet ground state for (4 a-4 c)- with the singlet-triplet energy gap of 17-24 kcal mol-1 .

Crystalline phosphino-functionalized mesoionic olefins (p-MIOs).

Phosphino-functionalized mesoionic olefins (p-MIOs), (iMIC)CHR (iMIC = PhC{N(Dipp)}2C(PPh2)C, Dipp = 2,6-iPr2C6H3; R = H 4a or Ph 4b), derived from a 1,3-imidazole-based mesoionic carbene (iMIC) are reported. The p-MIOs 4a (blue) and 4b (green) are crystalline solids and have been characterized by NMR spectroscopy and X-ray diffraction as well as DFT calculations. The calculated proton affinities of 4a (291.3 kcal mol-1) and 4b (288.1 kcal mol-1) support their remarkable basicity that exceeds that of classical NHCs. Treatment of 4a with (Me2S)AuCl (and AgOTf) affords the dinuclear gold compounds [(4a)Au](X)2 (5-X) (X = Cl or OTf) with a short Au⋯Au distance of 3.130(2) Šfor 5-Cl. The reaction of 4a with the main-group reagent PhBCl2 yields the boronium cation [(4a)BPhCl]Cl (6).

Nickel-Catalyzed Intramolecular 1,2-Aryl Migration of Mesoionic Carbenes (iMICs).

Intramolecular 1,2-Dipp migration of seven mesoionic carbenes (iMICAr ) 2 a-g (iMICAr =ArC{N(Dipp)}2 CHC; Ar=aryl; Dipp=2,6-iPr2 C6 H3 ) under nickel catalysis to give 1,3-imidazoles (IMDAr ) 3 a-g (IMDAr =ArC{N(Dipp)CHC(Dipp)N}) has been reported. The formation of 3 indicates the cleavage of an N-CDipp bond and the subsequent formation of a C-CDipp bond in 2, which is unprecedented in NHC chemistry. The use of 3 in accessing super-iMICs (5) (S-iMIC=ArC{N(Dipp)N(Me)C(Dipp)}C) has been shown with selenium (6), gold (7), and palladium (8) compounds. The quantification of the stereoelectronic properties reveals the superior σ-donor strength of 5 compared to that of classical NHCs. Remarkably, the percentage buried volume of 5 (%Vbur =45) is the largest known amongst thus far reported iMICs. Catalytic studies show a remarkable activity of 5, which is consistent with their auspicious stereoelectronic features.

Fluorogenic Diversification of Unprotected Bromotryptophan by Aqueous Mizoroki-Heck Cross-Coupling.

Fluorescent styryl-tryptophans have been synthesized by a Mizoroki-Heck cross-coupling from unprotected bromotryptophan in aqueous medium showing promising spectrophotometric properties for possible application in fluorescence labelling of biomolecules. Moreover, this strategy permits a modular combination of biocatalytic halogenation by using immobilized FAD-dependent tryptophan halogenases and Pd-mediated chemocatalysis in a multistep one-pot process.