Coordination and Stabilization of a Lithium Ion with a Silylene

Abstract

Herein, we report the stabilization of lithium‐ion as the source of lithium to use as a trans‐metalation reagent [{PhC(NtBu)2Si(tBu)Li}2I(tBuN)2CPh] (1). The reaction of 3 equivalents of the LSitBu (L=PhC(NtBu)2) and lithium iodide at low temperature leads to a silylene stabilized lithium‐ion with an additional coordination of amidinate ligand. Compound 1 shows two four membered and one six membered ring as confirmed by QTAIM calculations. Whereas the reaction of the LSiCl with 1.5 equivalents of carbodiimide (CyN)2C at room temperature affords compound [PhC(NtBu)2Si(Cl)(NCy)2NCy] (2) with the CN2SiN2C skeleton containing silicon as a central atom. Both the compounds were fully characterized by NMR, mass spectrometry, X‐ray crystallographic analysis, and quantum mechanical calculations.

Synthesis and Reactivity of Base-Stabilized and Base-Free Silaimidoyl Bromides

“…Slow evaporation of the solvent yielded red crystals, and the single-crystal X-ray diffraction (XRD) experiment confirmed the structure of silaimine 2 , reminiscent of the postulated IntB (Figure ). Unlike in the literature-known examples, ,, in this case, the isonitrile functions as a donor to the silicon atom and cannot be removed from the compound without decomposition. Although the silicon atom is clearly tetracoordinated, its coordination by the carbazolyl ligand, the bromine atom, and the N1 atom is close to trigonal planar with a sum of the bond angles of 349°.…”

“…19,21−25 The reaction of silylenes with carbodiimides is an alternative way to access silaimines, thereby avoiding the use of hazardous organoazides. Roesky showed that both amidinato chlorosily- 27 Thus, as the experimental results indicate, a balanced steric bulk of the combined silylenes and azides is required for the stabilization of the Si�N bond.…”

“…The reaction of silylenes with carbodiimides is an alternative way to access silaimines, thereby avoiding the use of hazardous organoazides. Roesky showed that both amidinato chlorosilylene and the NHC-stabilized bischlorosilylene IDippSiCl 2 form the corresponding silaimines with (DippN) 2 C under the elimination of isocyanide, yielding VII and VIII , respectively. , When (CyN) 2 C is used, however, 1.5 equiv of the carbodiimide react to form a CN 2 SiN 2 C skeleton with a central silicon atom ( IX ) . Thus, as the experimental results indicate, a balanced steric bulk of the combined silylenes and azides is required for the stabilization of the SiN bond.…”

Compounds with Alternating Single and Double Bonds of Antimony and Silicon; Isoelectronic to Ethane-1,2-diimine

“…This property causes the Sb–Si π-bonding to be polarized, which can readily lead to dimerization or polymerization . A great variety of alkene analogues featuring a heteronuclear double bond between the identically heavier Group 14–15 elements was synthesized following the original discovery of the first stable silaimine >SiN and silaphosphene >SiP derivatives. − The search for the formation of multiply bonded silicon compounds with Group 15 elements remains unbroken throughout the last decades and even is intensified for this most fascinating topic in silicon chemistry . Last year, major results could be added to the isolation of silylene moieties bound to Group 15 elements .…”

Synthesis and Characterization of Substituted Phosphasilenes and its Rare Homologue Stibasilene >Si=Sb−

“…Such lack of isolable stiba‐ and bismasilenes provoked us to challenge the preparation of a doubly bonded heavy analogues R 2 Si=Ear (E=P, Sb, Bi), of the Schiff base derivatives. Surprisingly the reactivity of amidinate stabilized silylene towards antimony‐based compound remained almost unexplored [10b–h] . Which embarked us to synthesize phosphasilenes >Si=P− and its heavy homologue stibasilene >Si=Sb− using advantage of the above‐described unified synthetic approach, unfortunately could not obtained the bismasilenes.…”