Chelating N-Heterocyclic Silylenes as Steering Ligands in Catalysis

Gallego, Daniel; Blom, Burgert; Tan, Gengwen; Drieß, Matthias

doi:10.1016/b978-0-12-409547-2.11449-0

Cited by 2 publications

(1 citation statement)

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“…Over the past decades, N -heterocyclic silylenes (NHSi) have been intensively studied and became more and more a suitable alternative for traditional ligands in organometallic chemistry, not only but primarily in their role as strong σ-donors in metal complexes. − For several years, only group 5–10 transition-metal complexes stood in the focus of research, whereas group 11 or 12 metal complexes were still comparatively rare . Early examples of Frenking and Boehme about theoretical analysis of coinage metal NHSi complexes were followed by single synthetic approaches by Lappert et al, who, for example, published a tetrahedral copper NHSi complex employing the Arduengo type of motif ( I , Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Side-Arm Functionalized Silylene Copper(I) Complexes in Catalysis

2019

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A convenient new method was added to the toolbox of the ligand design of N-heterocyclic silylenes and their transition-metal complexes. Herein we report on six novel compounds of two novel classes of copper(I) complexes based on the benzamidinate silylene (Cl)Si(PhC(NtBu)2). By taming the high reactivity of the free electron pair of the Si(II) atom via a preset metalation with a desired metal precursor (in this case copper(I) halides) we can easily introduce novel pyridyl-based groups in the subsequent functionalization of the chloro group and undergo coordination of the metal atom at the same time. The resulting pseudocubane-like tetramer [XCu(I) ← (Cl)Si(PhC(NtBu)2)]4 2a–2c and the trinuclear dimer [(XCu(I))3(PyNMes)Si(PhC(NtBu)2)] 3a–3c (with X = Cl (2a/3a), Br (2b/3b), I (2c/3c)) were fully characterized via X-ray diffraction analysis, NMR spectroscopy, mass spectrometry, and elemental analysis. Moreover, we took a look into the catalytic potential of the Cu(I) complexes 2b and 3b by testing them under the conditions of the renowned copper(I)-catalyzed alkyne–azide cycloaddition and observed an increased activity of the functionalized species.

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Section: Introductionmentioning

confidence: 99%

Side-Arm Functionalized Silylene Copper(I) Complexes in Catalysis

2019

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Silicon(II) Bis(trimethylsilyl)amide (LSiN(SiMe₃)₂, L = PhC(NtBu)₂) Supported Copper, Silver, and Gold Complexes

et al. 2015

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The reactions of silicon(II) bis(trimethylsilyl)amide (1; LSiN(SiMe3)2, L = PhC(NtBu)2) with the readily available CuI, AgOTf (Tf = SO2CF3), AgNO3, and AuCl(SMe2) have been reported, which resulted in a series of silylene–coinage-metal complexes (2–5) with Si(II)→coinage-metal bonds. Each compound has been characterized by multinuclear NMR spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray diffraction studies. X-ray analyses of 2 and 3 showed that they are dimeric in nature, featuring four-membered Cu2I2 and Ag2O2 rings, respectively. However, 4 and 5 are mononuclear complexes with a silylene ligand and possess only one SiII→Ag or SiII→Au bond, respectively. Prior to our contribution, there have been very few structurally authenticated silylene–silver and silylene–gold complexes known. Therefore, 2–5 are noteworthy additions to the Si(II)–coinage-metal complexes.

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Chelating N-Heterocyclic Silylenes as Steering Ligands in Catalysis

Cited by 2 publications

References 48 publications

Side-Arm Functionalized Silylene Copper(I) Complexes in Catalysis

Side-Arm Functionalized Silylene Copper(I) Complexes in Catalysis

Silicon(II) Bis(trimethylsilyl)amide (LSiN(SiMe₃)₂, L = PhC(NtBu)₂) Supported Copper, Silver, and Gold Complexes

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Chelating N-Heterocyclic Silylenes as Steering Ligands in Catalysis

Cited by 2 publications

References 48 publications

Side-Arm Functionalized Silylene Copper(I) Complexes in Catalysis

Side-Arm Functionalized Silylene Copper(I) Complexes in Catalysis

Silicon(II) Bis(trimethylsilyl)amide (LSiN(SiMe3)2, L = PhC(NtBu)2) Supported Copper, Silver, and Gold Complexes

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Silicon(II) Bis(trimethylsilyl)amide (LSiN(SiMe₃)₂, L = PhC(NtBu)₂) Supported Copper, Silver, and Gold Complexes