The isolation of silicon analogues of phenyl anions such as (CH) and (CH) is challenging owing to their extremely high reactivity associated with their silylene character and weak C-Si π-interaction. Herein, we report the first annulated 1,4-disilabenzene-1,4-diide compound [(ADC)Si] () based on anionic dicarbene (ADC) scaffolds (ADC = PhC{N(Dipp)C}; Dipp = 2,6-PrCH) as a green-yellow crystalline solid. Compound is prepared by KC reduction of the Si(IV) chloride [(ADC)SiCl] () or the cyclic bis-chlorosilylene [(ADC)SiCl] (), which are also prepared for the first time.
View Article and Find Full Text PDFHerein, reactivity studies of a cyclic bis-hydridostannylene [(ADC)SnH] (1-H) (ADC=PhC{(NDipp)C}; Dipp=2,6-iPrCH) with various unsaturated organic substrates are reported. Reactions of terminal alkynes (RC≡CH) with 1-H afford mixed acetylide-vinyl-functionalized bis-stannylenes via dehydrogenation and hydrostannylation. Treatment of 1-H with PhC≡CCH gives a unique distannabarrelene via dehydrogenative C-H stannylation and hydrostannylation of the C≡CCH moiety.
View Article and Find Full Text PDFDecarbonylation of a cyclic bis-phosphaethynolatostannylene [(ADC)Sn(PCO)] based on an anionic dicarbene framework (ADC = PhC{N(Dipp)C} ; Dipp = 2,6-iPr C H ) under UV light results in the formation of a Sn P cluster compound [(ADC)SnP] as a green crystalline solid. The electronic structure of [(ADC)SnP] is analyzed by quantum-chemical calculations. At room temperature, [(ADC)SnP] reversibly binds with CO and forms [(ADC) {SnOC(O)P}SnP].
View Article and Find Full Text PDFMesoionic dithiolates [(MIDt )Li(LiBr) (THF) ] (MIDt ={SC(NDipp)} CAr; Dipp=2,6-iPr C H ; Ar=Ph 3 a, 3-MeC H (3-Tol) 3 b, 4-Me NC H (DMP) 3 c) and [(MIDt )Li(THF) ] (4) are readily accessible (in≥90 % yields) as crystalline solids on treatments of anionic dicarbenes Li(ADC ) (2 a-c) (ADC ={C(NDipp) } CAr) with elemental sulfur. 3 a-c and 4 are monoanionic ditopic ligands with both the sulfur atoms formally negatively charged, while the 1,3-imidazole unit bears a formal positive charge. Treatment of 4 with (L)GeCl (L=1,4-dioxane) affords the germylene (MIDt )GeCl (5) featuring a three-coordinated Ge atom.
View Article and Find Full Text PDFThe cyclic Ge(I) compound [(ADC)Ge] () (ADC = {CN(Dipp)}CPh, Dipp = 2,6-PrCH) containing a 6π-electron CGe framework has been isolated as a red crystalline solid. CASSCF calculations reveal a closed-shell singlet ground state for with a considerable diradical character ( = 34%). Thus, the diradicaloid readily splits dihydrogen at room temperature to yield the elusive bis-hydridogermylene [(ADC)GeH] ().
View Article and Find Full Text PDFThe first C5-protonated abnormal N-heterocyclic carbene (aNHC), PhC{N(2,6-iPr C H )} CHC: (4) is readily accessible by C4-deprotonation of [ArC{N(2,6-iPr C H )} CHCH]X (3 a-X) (Ar=Ph, X=Br or I) with a base. The aNHC 4 is stable at 298 K in [D ]THF solution and has been spectroscopically characterized. The facile availability of 4 enables the synthesis of a series of main-group compounds as well as transition-metal complexes featuring a new phosphorus-aNHC hybrid ligand.
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