Synthesis and structures of 3-sila-β-diketiminato complexes of the coinage metals

Farwell, James D.; Hitchcock, Peter B.; Läppert, Michael F.; Protchenko, Andrey V.

doi:10.1016/j.jorganchem.2007.07.012

Cited by 10 publications

(5 citation statements)

References 43 publications

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“… Two silylene units are bound to the four-membered Ag 2 O 2 core, in which the two O atoms from the OTf groups are not in the same plane of the Ag atoms. The Si–Ag bond lengths (2.337(2) and 2.346(2) Å) are shorter than those of G (2.4015(16) Å) and the reported silylsilver complex (2.483(2) Å), which are presumably a reflection of the substituents on the Si(II) center. The substantially longer Si→Ag bond length in 3 in comparison to the Si→Cu bond in 2 and the Si→Au bond in 5 can be attributed to the electron-withdrawing nature of the triflate groups.…”

Section: Resultsmentioning

confidence: 69%

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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Section: Resultsmentioning

confidence: 69%

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 structure of 10 was confirmed by a single-crystal X-ray diffraction experiment, which revealed the presence of a SiHTrip unit bridging Cp*(IXy)(H)Ru and AgOTf fragments (Figure ), resulting in Ru–Si and Ru–Ag bond distances of 2.264(1) and 2.6813(8) Å, respectively. The Ag–Si distance of 2.562(1) Å is slightly longer than that found in the only other structurally characterized silver–silicon-bonded compound, Ag{Si(SiMe 3 )[C(Xyl)NSiMe 3 ] 2 Li} 2 (μ-I) [2.482(1) Å], and is roughly equal to the sum of covalent radii of silicon and silver (2.56 Å) . Furthermore, the hydride ligand, which was located and refined, adopts a position that bridges the Ru and Si centers ( J SiH = 36.6 Hz).…”

Section: Results and Discussionmentioning

confidence: 89%

Cyclometalated N-Heterocyclic Carbene Complexes of Ruthenium for Access to Electron-Rich Silylene Complexes That Bind the Lewis Acids CuOTf and AgOTf

et al. 2014

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The synthesis of the cyclometalated complexes Cp*Ru(IXy-H) (2) [IXy = 1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene; IXy-H = 1-(2-CH2C6H3-6-methyl)-3-(2,6-dimethylphenyl)imidazol-2-ylidene-1-yl (the deprotonated form of IXy); Cp* = η(5)-C5Me5] and Cp*Ru(IXy-H)(N2) (3) was achieved by dehydrochlorination of Cp*Ru(IXy)Cl (1) with KCH2Ph. Complexes 2 and 3 activate primary silanes (RSiH3) to afford the silyl complexes Cp*(IXy-H)(H)RuSiH2R [R = p-Tol (4), Mes (5), Trip (6)]. Density functional theory studies indicated that these complexes are close in energy to the corresponding isomeric silylene species Cp*(IXy)(H)Ru═SiHR. Indeed, reactivity studies indicated that various reagents trap the silylene isomer of 6, Cp*(IXy)(H)Ru═SiHTrip (6a). Thus, benzaldehyde reacts with 6 to give the [2 + 2] cycloaddition product 7, while 4-bromoacetophenone reacts via C-H bond cleavage and formation of the enolate Cp*(IXy)(H)2RuSiH[OC(═CH2)C6H4Br]Trip (8). Addition of the O-H bond of 2,6-dimethylphenol across the Ru═Si bond of 6a gives Cp*(IXy)(H)2RuSiH(2,6-Me2C6H3O)Trip (9). Interestingly, CuOTf and AgOTf also react with 6 to provide unusual Lewis acid-stabilized silylene complexes in which MOTf bridges the Ru-Si bond. The AgOTf complex, which was crystallographically characterized, exhibits a structure similar to that of [Cp*((i)Pr3P)Ru(μ-H)2SiHMes](+), with a three-center, two-electron Ru-Ag-Si interaction. Natural bond orbital analysis of the MOTf complexes supported this type of bonding and characterized the donor interaction with Ag (or Cu) as involving a delocalized interaction with contributions from the carbene, silylene, and hydride ligands of Ru.

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“…and established by DOSY NMR. In contrast, the X‐ray crystal structure of 3 displays a centrosymmetric dimer with a Cu 2 Cl 2 diamond core . The Cu−Si distance (2.1905(9) Å) is marginally shorter than that reported for the monomeric silyl chlorocuprate based on ligand A (Scheme , 2.197(2) Å) and hence the shortest reported for copper silanides, presumably because of the large Si s character of the bonding orbital .…”

Section: Methodsmentioning

confidence: 99%

A Free Silanide from Nucleophilic Substitution at Silicon(II)

Witteman

Evers

Lutz

et al. 2018

Chemistry A European J

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A computationally guided synthetic route to a free silanide derived from tris(3‐methylindol‐2‐yl)methane ([(tmim)Si]−) through nucleophilic substitution on the SiII precursor (Idipp)SiCl2 is reported (Idipp=2,3‐dihydro‐1,3‐bis(2,6‐diisopropylphenyl)‐1H‐imidazol‐2‐ylidene). This approach circumvents the need for strained tetrahedral silanes as synthetic intermediates. Computational investigations show that the electron‐donating properties of [(tmim)Si]− are close to those of PMe3. Experimentally, the [(tmim)Si]− anion is shown to undergo clean complexation to the base metal salts CuCl and FeCl2, demonstrating the potential utility as a supporting ligand.

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Synthesis and structures of 3-sila-β-diketiminato complexes of the coinage metals

Cited by 10 publications

References 43 publications

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

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

Cyclometalated N-Heterocyclic Carbene Complexes of Ruthenium for Access to Electron-Rich Silylene Complexes That Bind the Lewis Acids CuOTf and AgOTf

A Free Silanide from Nucleophilic Substitution at Silicon(II)

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Synthesis and structures of 3-sila-β-diketiminato complexes of the coinage metals

Cited by 10 publications

References 43 publications

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

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

Cyclometalated N-Heterocyclic Carbene Complexes of Ruthenium for Access to Electron-Rich Silylene Complexes That Bind the Lewis Acids CuOTf and AgOTf

A Free Silanide from Nucleophilic Substitution at Silicon(II)

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

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