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.

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.

1,3-Imidazole-Based Mesoionic Carbenes and Anionic Dicarbenes: Pushing the Limit of Classical N-Heterocyclic Carbenes.

Classical N-heterocyclic carbenes (NHCs) featuring the carbene center at the C2-position of 1,3-imidazole framework (i.e. C2-carbenes) are well acknowledged as very versatile neutral ligands in molecular as well as in materials sciences. The efficiency and success of NHCs in diverse areas is essentially attributed to their persuasive stereoelectronics, in particular the potent σ-donor property. The NHCs with the carbene center at the unusual C4 (or C5) position, the so-called abnormal NHCs (aNHCs) or mesoionic carbenes (iMICs), are however superior σ-donors than C2-carbenes. Hence, iMICs have substantial potential in sustainable synthesis and catalysis. The main obstacle in this direction is rather demanding synthetic accessibility of iMICs. The aim of this review article is to highlight recent advances, particularly by the author's research group, in accessing stable iMICs, quantifying their properties, and exploring their applications in synthesis and catalysis. In addition, the synthetic viability and use of vicinal C4,C5-anionic dicarbenes (ADCs), also based on an 1,3-imidazole framework, are presented. As will be apparent on following pages, iMICs and ADCs hold potentials in pushing the limit of classical NHCs by enabling access to conceptually new main-group heterocycles, radicals, molecular catalysts, ligands sets, and more.

Isolation of an Anionic Dicarbene Embedded Sn2 P2 Cluster and Reversible CO2 Uptake.

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.