N-Heterocyclic Carbene Stabilized Dichlorosilaimine IPr·Cl₂SiNR

N-Heterocyclic carbene stabilized dichlorosilaimine IPr·Cl2SiN(Diip) (2) has been synthesized by the reaction of dichlorosilylene IPr·SiCl2 (1) with bis(2,6-diisopropylphenyl)carbodiimide (IPr = :C[N(2,6-i-Pr2-C6H3)CH]2, Diip = 2,6-i-Pr2-C6H3). Reaction of 1 with terphenyl azides also affords dichlorosilaimines IPr·Cl2SiN(2,6-Diip2-C6H3) (3) and IPr·Cl2SiN(2,6-Triip2-C6H3) (4) (Triip = 2,4,6-i-Pr3-C6H2). 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

A Facile Route to Functionalized N-Heterocyclic Carbenes (NHCs) with NHC Base-Stabilized Dichlorosilylene

Reaction of IPr·SiCl2 (1) [IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene] with 1-azidoadamantane leads to functionalized N-heterocyclic carbene (NHC) 2. Silyl-substituted NHC 2 reacts easily with 1-azidoadamantane to form triazene 3, in which the exocyclic CN bond is slightly shorter than those of regular NHC-derived triazines. 2 could serve as a promising ligand for transition metals

N-Heterocyclic Carbene Stabilized Dichlorosilaimine IPr·Cl₂SiNR

N-Heterocyclic carbene stabilized dichlorosilaimine IPr·Cl2SiN(Diip) (2) has been synthesized by the reaction of dichlorosilylene IPr·SiCl2 (1) with bis(2,6-diisopropylphenyl)carbodiimide (IPr = :C[N(2,6-i-Pr2-C6H3)CH]2, Diip = 2,6-i-Pr2-C6H3). Reaction of 1 with terphenyl azides also affords dichlorosilaimines IPr·Cl2SiN(2,6-Diip2-C6H3) (3) and IPr·Cl2SiN(2,6-Triip2-C6H3) (4) (Triip = 2,4,6-i-Pr3-C6H2). 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

N-Heterocyclic Carbene Stabilized Dichlorosilaimine IPr·Cl₂SiNR

N-Heterocyclic carbene stabilized dichlorosilaimine IPr·Cl2SiN(Diip) (2) has been synthesized by the reaction of dichlorosilylene IPr·SiCl2 (1) with bis(2,6-diisopropylphenyl)carbodiimide (IPr = :C[N(2,6-i-Pr2-C6H3)CH]2, Diip = 2,6-i-Pr2-C6H3). Reaction of 1 with terphenyl azides also affords dichlorosilaimines IPr·Cl2SiN(2,6-Diip2-C6H3) (3) and IPr·Cl2SiN(2,6-Triip2-C6H3) (4) (Triip = 2,4,6-i-Pr3-C6H2). 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

A Facile Route to Functionalized N-Heterocyclic Carbenes (NHCs) with NHC Base-Stabilized Dichlorosilylene

Reaction of IPr·SiCl2 (1) [IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene] with 1-azidoadamantane leads to functionalized N-heterocyclic carbene (NHC) 2. Silyl-substituted NHC 2 reacts easily with 1-azidoadamantane to form triazene 3, in which the exocyclic CN bond is slightly shorter than those of regular NHC-derived triazines. 2 could serve as a promising ligand for transition metals

A Facile Route to Functionalized N-Heterocyclic Carbenes (NHCs) with NHC Base-Stabilized Dichlorosilylene

Reaction of IPr·SiCl2 (1) [IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene] with 1-azidoadamantane leads to functionalized N-heterocyclic carbene (NHC) 2. Silyl-substituted NHC 2 reacts easily with 1-azidoadamantane to form triazene 3, in which the exocyclic CN bond is slightly shorter than those of regular NHC-derived triazines. 2 could serve as a promising ligand for transition metals

Reactions of Stable <i>N</i>-Heterocyclic Silylenes with Ketones and 3,5-Di-<i>tert</i>-butyl-<i>o</i>-benzoquinone

The reactions of L [PhC(NtBu)2SiCl] and L′ [CH{(CCH2)(CMe)(2,6-iPr2C6H3N)2}Si] with monoketones and quinone have been examined. The reaction of L with 2-adamantanone furnishes a [1 + 2]–cycloaddition product 1, whereas with 3,5-di-tert-butyl-o-benzoquinone leads to the [1 + 4]–cycloaddition product 2. The treatment of L′ with 3,5-di-tert-butyl-o-benzoquinone gives [1 + 4]–cycloaddition product 3, and the reaction with acylferrocene yields compound 4. Compounds 1–4 were characterized by single crystal X-ray structural analysis, NMR spectroscopy, EI–MS spectrometry, and elemental analysis

Facile Access to the Functionalized N-Donor Stabilized Silylenes PhC(N<i>t</i>Bu)₂SiX (X = PPh₂, NPh₂, NCy₂, N<i>i</i>Pr₂, NMe₂, N(SiMe₃)₂, O<i>t</i>Bu)

Reactions of silylenes with organic substrates generally lead to silicon­(IV) compounds. Ligand substitution at the silicon­(II) atom of silylene, without changing the formal +2 oxidation state, is very rare. We report herein a straightforward route to functionalized silylenes LSiX (L = PhC­(NtBu)2 and X = PPh2 (1), NPh2 (2), NCy2(3), NiPr2 (4), NMe2 (5), N­(SiMe3)2 (6), OtBu (7)). Silylenes 1–7 have been prepared in quantitative yield by a modified ligand exchange reaction of PhC­(NtBu)2SiCl (LSiCl) with the corresponding lithium or potassium salts. Compounds 1–7 were characterized by spectroscopic and spectrometric techniques. Single-crystal X-ray structures of 1, 3, and 4 were determined

Reactivity Studies of a Stable N‑Heterocyclic Silylene with Triphenylsilanol and Pentafluorophenol

The reaction of the stable N-heterocyclic silylene [CH­{(CCH2)­(CMe)­(2,6-iPr2C6H3N)2}­Si] (1) with triphenylsilanol and pentafluorophenol in a 1:2 molar ratio resulted in quantitative yields of the pentacoordinate silicon-containing compounds [CH­{(CMe)2(2,6-iPr2C6H3N)2}­Si­(H)­{OSiPh3}2] (2) and [CH­{(CMe)2(2,6-iPr2C6H3N)2}­Si­(H)­{OC6F5}2] (3), respectively. Compounds 2 and 3 were formed by O–H bond activation of triphenylsilanol and pentafluorophenol. They were characterized by elemental analysis, NMR spectroscopy, and EI-MS spectrometry. In their solid-state structures the silicon atom is tetracoordinate in 2, whereas it is pentacoordinate in 3