Facile activation of inert small molecules using a 1,2-disilylene

Abstract

Reactions of the known amidinate stabilised 1,2-disilylene, [{ArC(NDip)2}Si]2 1 (Dip = 2,6-diisopropylphenyl, Ar = 4-C6H4But) with a series of inert, unsaturated small molecule substrates have been carried out. Compound 1...

Applications of low-valent compounds with heavy group-14 elements

“…Jones and co-workers prepared a dimer of arylamidinato-silylene ((ArC(NDipp) 2 )Si) 2 (Ar = 4-C 6 H 4 t Bu) Si26 via the reduction of the corresponding trichlorosilane derivative with [{( Mes NacNac)Mg} 2 ] in toluene at room temperature, affording Si26 as a deep-blue crystalline solid (Scheme 18). 55,56…”

“…The tri-oxo disilicon( iv ) intermediate was created when the disilylene reduced three molecules of CO 2 to create the oxo-dicarbonate product (Scheme 195). The generation of a gaseous byproduct was observed, which was assumed to be CO. 56…”

“…54 Jones and co-workers prepared a dimer of arylamidinatosilylene ((ArC(NDipp) 2 )Si) 2 (Ar = 4-C 6 H 4 t Bu) Si26 via the reduction of the corresponding trichlorosilane derivative with [{( Mes Nac-Nac)Mg} 2 ] in toluene at room temperature, affording Si26 as a deep-blue crystalline solid (Scheme 18). 55,56 A spacer-separated bis(silylene), N,N-bis(silylenyl)aniline Si27, was reported by Driess and co-workers by reacting PhNLi 2 with two equivalents of Si2 (Scheme 19). 57 2.1.3 Low-valent silicon cations and silylone species.…”

“…The trioxo disilicon(IV) intermediate was created when the disilylene reduced three molecules of CO 2 to create the oxo-dicarbonate product (Scheme 195). The generation of a gaseous byproduct was observed, which was assumed to be CO. 56 Scheme 191 CO 2 activation by compounds Si6a and Si6b. Inoue and co-workers isolated two four-coordinate silaacylium ions, Si84a and Si84b, via the reduction of carbon dioxide with NHC-stabilized silyliumylidene ions Si31 and Si32, respectively (Scheme 196).…”

Small molecules (CO2, iPrNCO, and iPrNCNiPr) activation by the metallomimetics (μ‐Hydrido) diborane anion: A DFT investigation on mechanism and chemoselectivity controlling

“…Moreover, transition‐metal complexes replaced by main‐group molecules can avoid the high cost and environmental pollution 9,10 . This discovery has inspired great interest in investigating the possibility of hitherto transition‐metal‐exclusive reactions using purely main‐group compounds, and this new chemical field is termed “main‐group metallomi‐metics.” 11,12 Heavier Group 14 dimetallynes or dimetallenes, 12–16 compounds with heavier low‐valent p‐block elements, 9 ambiphiles FLPs, 17,18 singlet carbenes, 19,20 constrained phosphines, 21 and boron‐base molecules 22 have been proven to exhibit the chemical behavior of transition metals. Among them, boron‐base systems have gained wide attention due to their low toxicity, low cost, atypical oxidation states and molecular arrangements 22 .…”