N-Heterocyclic Carbene Stabilized Dichlorosilaimine IPr·Cl₂Si═NR

Abstract

N-Heterocyclic carbene stabilized dichlorosilaimine IPr 3 Cl 2 SidN(Diip) (2) has been synthesized by the reaction of dichlorosilylene IPr 3 SiCl 2 (1) with bis(2,6-diisopropylphenyl)carbodiimide (IPr = :C[N(2,6-i-Pr 2 -C 6 H 3 )CH] 2 , Diip = 2,6-i-Pr 2 -C 6 H 3 ). Reaction of 1 with terphenyl azides also affords dichlorosilaimines IPr 3 Cl 2 SidN(2,6-Diip 2 -C 6 H 3 ) (3) and IPr 3 Cl 2 SidN(2,6-Triip 2 -C 6 H 3 ) ( 4) (Triip = 2,4,6-i-Pr 3 -C 6 H 2 ). Compounds 2-4 are stable under an inert atmosphere and were characterized by elemental analysis and NMR spectroscopic studies. The molecular structures of 2-4 were determined by single-crystal X-ray analysis.

Facile Access to an NHC‐Coordinated Silicon Ring Compound with a Si=N Group and a Two‐Coordinate Silicon Atom

“…The Si4=N7 (1.625(2) Å) bond length is at the upper range of those found in silaimines (1.550–1.611 Å) . Silaimines were synthesized by the addition of azides to a silylene,–,, or more recently by the addition of SiCl 4 to an NHC‐coordinated amidochloro‐substituted silylene or SiI 4 to an N(SiMe 3 ) 2 and amidinato‐substituted silylene . In addition, unsaturated compounds such as isonitriles and acetylenes reacted with NHC‐coordinated amidochloro‐substituted silylenes to yield silaimines ,.…”

A Dimer of Silaisonitrile with Two‐Coordinate Silicon Atoms

“…[21] This result is in contrast to the carbon analogues. [22] Despite the remarkable theoretical contributions by Apeloig and others [20,21] on the relative stability of silanitrile (RSiN) and silaisonitrile (RNSi), no silaisonitrile or silanitrile has been reported to date that is stable at room temperature.Very recently, we reported NHC-stabilized dichlorosilaimine [23] IPr·Cl 2 Si = NAr (1; IPr= 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, Ar = 2,6-bis(2,4,6-triisopropylphenyl)phenyl), which was prepared by the reaction of IPr·SiCl 2 [24] with ArN 3 . Herein, we present the reduction of dichlorosilaimine 1 with KC 8 to afford a dimeric silaisonitrile (ArNSi:) 2 (3; Scheme 1).…”

Extremely bulky amide ligands in main group chemistry

“…Imides [(2,6-Ar 2 C 6 H 3 )N] 2À can stabilise the dichlorosilaimine complexes IPrÁCl 2 SiQN(2,6-Ar 2 C 6 H 3 ) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, Ar = Dipp 15, Trip 16) 38 (18) and PhC(N t Bu) 2 (Cl)-SiNC 6 H 3 -2,6-Trip 2 (19) can also be synthesised. 41 The reactions of the lanthanide silylamides Ln{N(SiHMe 2 ) 2 } 3 (THF) 2 with the aniline 2,6-Mes 2 C 6 H 3 NH 2 affords LnN{SiMe 2 N(C 6 H 3 -2,6-Mes 2 )} 2 (Ln = Ce 20, Pr 21), which feature N-Si bonds, the tridentate ligands formed via a lanthanide-induced Si-H activation.…”

“…48 29 is formed in a mixture of cis and trans isomers. In the case of arsenic complex 30 the choice of reaction conditions and base is very important: use of DBU at warmer temperatures affords a complex mixture featuring 2-m-terphenyl-amino-2-arsa-3,7-diazatricyclo[5.4.1.0 3,12 ]dodec-3(12)enyliumchloride (37), and the use of LDA (lithium diisopropylamide) affords 2,6-Mes 2 C 6 H 3 N(H)As(Cl)N i Pr 2 (38). 47 The phosphorus compound 29 can be formed using NEt 3 as the base, but for the arsenic and bismuth analogues only DBU (DBU = 1,8diazabicyclo [5.4.0]undec-7-ene) has been successfully employed thus far.…”