Taming a silyldiium cation and its reactivity towards sodium phosphaethynolate

Hermannsdorfer, André; Stephan, Douglas W.; Drieß, Matthias

doi:10.1039/c8cc07632d

Cited by 11 publications

(14 citation statements)

References 39 publications

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“…[5,6] Other silicon(IV)based LAs are routinely used in organic synthesis, with the commercially available TMSOTf (TMS = Me 3 Si) arguably being prevalent, [7] but far from being a LSA. [3] Bis-and tris(triflate) silanes potentially represent stronger LAs, but have mainly served as building blocks for polysilane syntheses [8,9] or as precursors for silicon-based polycations [10,11] with cleavage of the SiÀOTf bonds. Donor-free Si(OTf) 4 has not been isolated to date, [9] but recently, a high FIA was calculated for Si(OTf) 4 suggesting its Lewis superacidity.…”

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confidence: 99%

Silicon Tetrakis(trifluoromethanesulfonate): A Simple Neutral Silane Acting as a Soft and Hard Lewis Superacid

Drieß

Hermannsdorfer

2021

Angew Chem Int Ed

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A facile synthesis and isolation of pristine silicon tetrakis(trifluoromethanesulfonate), Si(OTf) 4 , is reported, acting as the first neutral silicon-based Lewis superacid suitable towards soft and hard Lewis bases. Its OTf groups have a dual function: they are excellent leaving groups and modulate the degree of reactivity towards soft and hard Lewis bases. Exposed to soft Lewis donors, Si(OTf) 4 leads to [L 2 Si(OTf) 4 ] complexes (L = isocyanide, thioether and carbonyl compounds) with retention of all SiÀOTf bonds. In contrast, it can cleave CÀX bonds (X = F, Cl) of hard organic Lewis bases with a high tendency to form SiX 4 (X = F, Cl) after halide/triflate exchange. Most notable, Si(OTf) 4 allows a gentle oxydefluorination of mono-and bis(trifluoromethyl)benzenes, resulting in the formation of the corresponding benzoylium species, which are stabilized by the weakly coordinating [Si(OTf) 6 ] dianion.

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confidence: 99%

Silicon Tetrakis(trifluoromethanesulfonate): A Simple Neutral Silane Acting as a Soft and Hard Lewis Superacid

Drieß

Hermannsdorfer

2021

Angew Chem Int Ed

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“…In some exceptional cases, the oxophilicity of the metal ion can instead deoxygenate [PCO] − , thus affording the metal‐oxide and cyaphide (CP − ) as the final fragments [10] . [PCO] − can also deliver a phosphorus atom to various electrophilic organic moieties, such as imidazolium, [11] silyldiium, [12] cyclopropenium, [13] chlorodiazaphospholidine, [14] cyclotrisilenes, [15] boroles, [16] and acyl chlorides, [17] inter alia [18] . Likewise, unsaturated organic molecules can engage the [PCO] − anion to give cyclooligomerizations that produce P‐containing heterocycles, [19] wherein the reaction generally proceeds through [2+2], [3+2], or [4+2] cycloaddition pathways [19f] …”

Section: Methodsmentioning

confidence: 99%

Phosphorus‐Atom Transfer from Phosphaethynolate to an Alkylidyne

et al. 2021

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A low‐spin and mononuclear vanadium complex, (Menacnac)V(CO)(η2‐P≡CtBu) (2) (Menacnac−=[ArNC(CH3)]2CH, Ar=2,6‐iPr2C6H3), was prepared upon treatment of the vanadium neopentylidyne complex (Menacnac)V≡CtBu(OTf) (1) with Na(OCP)(diox)2.5 (diox=1,4‐dioxane), while the isoelectronic ate‐complex [Na(15‐crown‐5)]{([ArNC(CH2)]CH[C(CH3)NAr])V(CO)(η2‐P≡CtBu)} (4), was obtained via the reaction of Na(OCP)(diox)2.5 and ([ArNC(CH2)]CH[C(CH3)NAr])V≡CtBu(OEt2) (3) in the presence of crown‐ether. Computational studies suggest that the P‐atom transfer proceeds by [2+2]‐cycloaddition of the P≡C bond across the V≡CtBu moiety, followed by a reductive decarbonylation to form the V−C≡O linkage. The nature of the electronic ground state in diamagnetic complexes, 2 and 4, was further investigated both theoretically and experimentally, using a combination of density functional theory (DFT) calculations, UV/Vis and NMR spectroscopies, cyclic voltammetry, X‐ray absorption spectroscopy (XAS) measurements, and comparison of salient bond metrics derived from X‐ray single‐crystal structural characterization. In combination, these data are consistent with a low‐valent vanadium ion in complexes 2 and 4. This study represents the first example of a metathesis reaction between the P‐atom of [PCO]− and an alkylidyne ligand.

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“…In 2018, Driess and co-workers reported the synthesis of a novel dicationic bis(NHC)-stabilised silyldiium complex ( 46 ; bis(NHC) = [CH 2 (NC 3 H 2 NDipp) 2 ], Dipp = 2,6- i Pr 2 C 6 H 3 ) by the reaction of Ph 2 Si(OTf) 2 with bis(NHC) in 1 : 1 molar ratio (Scheme 18b). 56 The 29 Si NMR of 4-coordinated Si appeared at δ = −36.7 ppm. The structure of 46 was rationalized by SCXRD analysis, which revealed that triflate anions and the central Si atom have no close contact.…”

Section: Reactivity Of Ocp− Towards Main-group Elementsmentioning

confidence: 99%

Recent advances in the chemistry of the phosphaethynolate and arsaethynolate anions

et al. 2022

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Taming a silyldiium cation and its reactivity towards sodium phosphaethynolate

Abstract: The synthesis of a (bis)NHC-silyldiium cation is reported and its reactivity towards sodium phosphaethynolate is shown to enable access to seven-membered heterocycles with P–X moieties (X = Si, P).

Cited by 11 publications

References 39 publications

Silicon Tetrakis(trifluoromethanesulfonate): A Simple Neutral Silane Acting as a Soft and Hard Lewis Superacid

Silicon Tetrakis(trifluoromethanesulfonate): A Simple Neutral Silane Acting as a Soft and Hard Lewis Superacid

Phosphorus‐Atom Transfer from Phosphaethynolate to an Alkylidyne

Recent advances in the chemistry of the phosphaethynolate and arsaethynolate anions

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