Catalytic Trimerization of Bis-silylated Diazomethane

Ibad, Muhammad Farooq; Langer, Peter; Reiß, Fabian; Schulz, Axel; Villinger, Alexander

doi:10.1021/ja308104k

Cited by 42 publications

(26 citation statements)

References 110 publications

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“…Therefore, cyanidation greatly increases the thermodynamic stability of all cyanidoborates relatively to the perfluorinated [BF 4 ]ion, or B(CN) 3 represents a very strong Lewis acid, which is much stronger than BF 3 . Furthermore, the CIA values supports this finding as they increase considerably along BF 3 Si-X-LA] (X = halogen or CN -) in the reactions of Me 3 Si-X with Lewis acids has been described previously, [52][53][54][55][56][57][58] and silylium ions have been isolated and used in catalysis. [59][60][61][62][63] Notably, the catalytic cycles in Scheme 7 are proposals based on the assumption that Lewis acids in the presence of a strong donor (such as Me 3 SiCN) form adducts (e.g., LA-NC-SiMe 3 ) that diminish their acidity compared with those of the free acids.…”

Section: Thermodynamic Considerations -Catalysissupporting

confidence: 59%

Lewis Acid Catalyzed Synthesis of Cyanidoborates

et al. 2016

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Section: Thermodynamic Considerations -Catalysissupporting

confidence: 59%

Lewis Acid Catalyzed Synthesis of Cyanidoborates

et al. 2016

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“…Startingf rom these parent compounds, derivativesc an be generated by successive substitution of protons with monovalentg roups. Sinces ilyliumi ons, in particular, the [Me 3 Si] + , are often referredt oa sl arge protons, [11][12][13][14][15][16] they have also been used to synthesize onium ions to stabilize them kinetically. Sinces ilyliumi ons, in particular, the [Me 3 Si] + , are often referredt oa sl arge protons, [11][12][13][14][15][16] they have also been used to synthesize onium ions to stabilize them kinetically.…”

Section: Introductionmentioning

confidence: 99%

On Silylated Oxonium and Sulfonium Ions and Their Interaction with Weakly Coordinating Borate Anions

Bläsing

Labbow

Michalik

et al. 2020

Chemistry A European J

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Attempts have been made to prepares alts with the labile tris(trimethylsilyl)chalconium ions, [(Me 3 Si) 3 E] + (E = O, S), by reacting[ Me 3 Si-H-SiMe 3 ][B(C 6 F 5 ) 4 ]a nd Me 3 Si[CB] (CB À = carborate = [CHB 11 H 5 Cl 6 ] À ,[ CHB 11 Cl 11 ] À )w ith Me 3 Si-E-SiMe 3 .I nt he reaction of Me 3 Si-O-SiMe 3 with [Me 3 Si-H-SiMe 3 ] [B(C 6 F 5 ) 4 ], al igand exchange was observed in the [Me 3 Si-H-SiMe 3 ] + cation leadingt ot he surprising formation of the persilylated [(Me 3 Si) 2 (Me 2 (H)Si)O] + oxonium ion in af ormal [Me 2 (H)Si] + instead of the desired [Me 3 Si] + transferr eaction. In contrast, the expected homoleptic persilylated [(Me 3 Si) 3 S] + ion was formed and isolated as [B(C 6 F 5 ) 4 ] À and [CB] À salt, when Me 3 Si-S-SiMe 3 was treated with either [Me 3 Si-H-SiMe 3 ] [B(C 6 F 5 ) 4 ]o rM e 3 Si[CB]. However, the addition of Me 3 Si[CB] to Me 3 Si-O-SiMe 3 unexpectedly led to the release of Me 4 Si with simultaneous formation of ac yclic dioxonium dicationo ft he type [Me 3 Si-mO-SiMe 2 ] 2 [CB] 2 in an anion-mediated reaction. DFT studies on structure, bonding and thermodynamicso f the [(Me 3 Si) 3 E] + and [(Me 3 Si) 2 (Me 2 (H)Si)E] + ion formation are presented as well as mechanistic investigationso nt he template-driven transformation of the [(Me 3 Si) 3 E] + ion into a cyclic dichalconium dication [Me 3 Si-mE-SiMe 2 ] 2 2 + . Scheme1.Synthesis of silylated chalconium salts with [B(C 6 F 5 ) 4 ] À as counterion (E = O, S; T= Me 3 Si, R = alkyl).

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“…Instead, recrystallization from Et 2 O yielded crystals of [Et 2 OSiMe 3 ][B(C 6 F 5 ) 4 ] · m ‐xylol. Although the compound [Et 2 OSiMe 3 ][B(C 6 F 5 ) 4 ] was already reported, its synthesis usually involved Me 3 Si + transfer reagents . It can be concluded that the intermediate, formed in the reaction of 1 with [Ag( m ‐xylol) 3 ][B(C 6 F 5 ) 4 ], is a strong silylating agent.…”

Section: Resultsmentioning

confidence: 99%

A Bismuth–Arene σ‐Complex – On the Edge of Menshutkin‐Type Complexes

et al. 2019

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Mes*N(SiMe 3 )BiCl 2 (1, Mes* = 2,4,6-tri-tert-butylphenyl) can be referred to as a hidden iminobismuthane, Mes*N=BiCl, which was thought to be generated in-situ upon Me 3 SiCl elimination triggered by a Lewis acid such as GaCl 3 . Therefore, the reactivity of aminobismuthane 1 was studied to find a synthesis route for the formation of a tetrazabismuthole in a [3+2] cycloaddition reaction with a covalently bound azide. However, reaction of 1 with GaCl 3 cleanly led to [Mes*N(SiMe 3 )-BiCl][GaCl 4 ] (2[GaCl 4 ]), a compound with a Bi-arene σ-complex. Utilizing Ag[WCA] salts (WCA = weakly coordinating anion) for [a]

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Catalytic Trimerization of Bis-silylated Diazomethane

Cited by 42 publications

References 110 publications

Lewis Acid Catalyzed Synthesis of Cyanidoborates

Lewis Acid Catalyzed Synthesis of Cyanidoborates

On Silylated Oxonium and Sulfonium Ions and Their Interaction with Weakly Coordinating Borate Anions

A Bismuth–Arene σ‐Complex – On the Edge of Menshutkin‐Type Complexes

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