Synthesis and Characterization of [PhC(NtBu)₂]SiCl: A Stable Monomeric Chlorosilylene

Abstract

The single life: The reaction of [PhC(NtBu)2]SiCl3 (1) with potassium afforded the monomeric chlorosilylene [PhC(NtBu)2]SiCl (2). The X‐ray crystal structure of 2 has been determined and natural‐bond‐orbital analysis carried out.

Synthesis and Reactivity of Functionalized Silicon(II) Compounds: Iminosilylene, Phosphinosilylene, Hydrosilylene, and Related Compounds

“…29b29f All of them were synthesized from salt metathesis reaction of alkali metal salts of phosphide with varying substituents either from the corresponding amidinate (PhC(NtBu) 2 ) stabilized monochlorosilylene (1719), 29b29d or from ImMe 4 (1,3,4,5-tetramethylimidazol-2-ylidene)} donor stabilized, aryl (20) 29e and amide substituted (21) 29f monochlorosilylene respectively. All of these compounds 1721 possess a tricoordinated pyramidalized silicon(II) center containing a lone pair of electrons.…”

“…12 Type III (Chart 7) containing amidinate stabilized silylene with varying substituent on nitrogen (7). 20 In 1977, the first NHSi-transition metal complex employing cyclic aminosilanes, 2-chloro-1,3-diphenyl-1,3-diaza-2-silacyclo-pentane, was reported. 56 This cyclic aminosilanes reacts with [Fe(CO) 5 ] to produce base stabilized [Fe(CO) 4 -(NHSi-3)] complex through CO elimination under photolytic conditions.…”

“…NHSi (chlorosilylene) 11 20 and NHC-stabilized dihalosilylenes 12 21 are both indispensable building blocks in synthetic chemistry (Chart 3). Owing to the presence of a labile SiCl bond in 11 has led to the introduction of several new heteroatom functionalities through salt metathesis reaction.…”

Ein cyclisches Silylon (“Siladicarben”) mit einem elektronenreichen Silicium(0)‐Atom

“…Neben dem erfolgreichen Zugang zu zweifach koordinierten cyclischen [1] und acyclischen Silylenen, [2] konnten sogar einige donorunterstützte dreifach koordinierte Silicium(II)-Spezies isoliert und strukturell charakterisiert werden. Herausragende Beispiele hierfür sind das Chlorosilylen PhC[N(tBu)] 2 SiCl [3] und der Dichlorosilylen-Komplex NHC-SiCl 2 A (Schema 1; NHC = N-heterocyclisches Carben, im Fall von A 1,3-Bis(2,6-diisopropylphenyl)imidazol-2-yliden). [4] Diese donorstabilisierten Chlorosilylene stellen attraktive Bausteine für die Synthese neuer siliciumhaltiger funktioneller Gruppen dar.…”

“…Zuvor hatten wir bereits gezeigt, dass sich das Bis(carben) 1 zur Synthese des isolierbaren cyclischen Germadicarbens F eignet (Schema 1). [11] Hier berichten wir über [5] und anderen dreifach koordinierten Silicium(II)-Verbindungen [LSi(Ar)Cl (L = 1,3,4,5-Tetramethylimidazol-2-yliden, Ar = 2,6-Mes 2 C 6 H 3 , d = 1.34 ppm in C 6 D 6 ; Ar= 2,6-Trip 2 C 6 H 3 (Trip = 2,4,6-iPr 3 C 6 H 2 ), d = 0.77 ppm in C 6 D 6 , [12] d = 19.1 ppm in C 6 D 6 für A, [4] und d = 14.6 ppm für PhC[N(tBu)] 2 SiCl in C 6 D 6 , [3] ]. (2) ), [4] in B (2.172(2) ) [5] und in PhC[N(tBu)] 2 SiCl 2.156(1).…”