NHC‐stabilized Silicon(II) Halides: Reactivity Studies with Diazoalkanes and Azides

Arz, Marius I.; Hoffmann, David; Schnakenburg, Gregor; Filippou, Alexander C.

doi:10.1002/zaac.201600286

Cited by 13 publications

(8 citation statements)

References 128 publications

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“…Recently, the reactivity of the NHC-stabilized Si(II) diiodide 606 toward an azide and a diazoalkane was reported . Conversion of 606 with MesN 3 and ( p -Tol) 2 CN 2 affords the NHC-supported silaimine 544 and silazine 548 as already shown above.…”

Section: Nhc Complexes Of Main Group Elementsmentioning

confidence: 99%

“…Filippou et al recently synthesized the three additional NHC-supported silaimine compounds 544−546 (Figure 65). 578 These complexes symbolize the first NHC-stabilized silaimine derivatives including Si−I and Si−N 3 moieties. SC-XRD analysis revealed distorted tetrahedrally coordinated silicon nuclei with SiN double bonds varying from 1.568(4) to 1.608(1) Å.…”

Section: Chemical Reviewsmentioning

confidence: 99%

“…The NHC-supported silaimines 545 and 546 are obtained from the reaction of 664b with the azides MesN 3 and TMSN 3 in high yield. 578 Similarly, the diazoalkane (2,6-Mes 2 -C 6 H 3 )-HCN 2 reacts with the arylchlorosilylene NHC adducts 664 under formation of the NHC-stabilized silazines 547 (vide supra).…”

Section: Chemical Reviewsmentioning

confidence: 99%

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NHCs in Main Group Chemistry

et al. 2018

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Since the discovery of the first stable N-heterocyclic carbene (NHC) in the beginning of the 1990s, these divalent carbon species have become a common and available class of compounds, which have found numerous applications in academic and industrial research. Their important role as two-electron donor ligands, especially in transition metal chemistry and catalysis, is difficult to overestimate. In the past decade, there has been tremendous research attention given to the chemistry of low-coordinate main group element compounds. Significant progress has been achieved in stabilization and isolation of such species as Lewis acid/base adducts with highly tunable NHC ligands. This has allowed investigation of numerous novel types of compounds with unique electronic structures and opened new opportunities in the rational design of novel organic catalysts and materials. This Review gives a general overview of this research, basic synthetic approaches, key features of NHC-main group element adducts, and might be useful for the broad research community.

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Section: Nhc Complexes Of Main Group Elementsmentioning

confidence: 99%

Section: Chemical Reviewsmentioning

confidence: 99%

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NHCs in Main Group Chemistry

et al. 2018

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“…Also, we could demonstrate the recovery of silyliumylidene A from VIIIa-c by the treatment with AuI as well as chalcogen transfer reactions. dihydrophosphasilene reported by Driess and coworkers in 2015 [56,57] as well as the reaction towards diazoalkanes and azides presented by Filippou and coworkers [58] remain as the only reports regarding the reactivity of this species.…”

Section: Introductionmentioning

confidence: 96%

“…Subsequently, the mTer iPr -chlorosilylene was employed as the precursor for the preparation of a silylidyne complex Cp(CO) 2 Mo≡Si(mTer iPr ) [55]. The conversion of those chlorosilylenes with lithium diphenylphosphine and LiPH 2 to the corresponding phosphinosilylene and 1,2-dihydrophosphasilene reported by Driess and coworkers in 2015 [56,57] as well as the reaction towards diazoalkanes and azides presented by Filippou and coworkers [58] remain as the only reports regarding the reactivity of this species.…”

Section: Introductionmentioning

confidence: 99%

S–H Bond Activation in Hydrogen Sulfide by NHC-Stabilized Silyliumylidene Ions

et al. 2018

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Reactivity studies of silyliumylidenes remain scarce with only a handful of publications to date. Herein we report the activation of S-H bonds in hydrogen sulfide by mTer-silyliumylidene ion A (mTer = 2,6-Mes 2 -C 6 H 3 , Mes = 2,4,6-Me 3 -C 6 H 2 ) to yield an NHC-stabilized thiosilaaldehyde B. The results of NBO and QTAIM analyses suggest a zwitterionic formulation of the product B as the most appropriate. Detailed mechanistic investigations are performed at the M06-L/6-311+G(d,p)(SMD: acetonitrile/benzene)//M06-L/6-311+G(d,p) level of density functional theory. Several pathways for the formation of thiosilaaldehyde B are examined. The energetically preferred route commences with a stepwise addition of H 2 S to the nucleophilic silicon center. Subsequent NHC dissociation and proton abstraction yields the thiosilaaldehyde in a strongly exergonic reaction. Intermediacy of a chlorosilylene or a thiosilylene is kinetically precluded. With an overall activation barrier of 15 kcal/mol, the resulting mechanistic picture is fully in line with the experimental observation of an instantaneous reaction at sub-zero temperatures.

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Theoretical Evidence for the Utilization of Low‐Valent Main‐Group Complexes as Rare‐Synthon Equivalents

Benedek

Orbán

Szilvási

2017

Chemistry A European J

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We examine by the means of computational chemistry the ability of two phosphasilenes to transfer the phosphinidene moiety to four double bonded organic functional groups (>C=C<, -N=N-, >C=O, and >C=S) in the presence of different bulky ligands. We show that large bulky groups in the reactants can sterically prohibit the otherwise favored association of reactants and phosphasilenes and instead a new phosphinidene transfer reaction can occur. We find that the transfer reaction mechanism is generally present independent from the functional group and by introducing large enough trimethylsilyl or tert-butyl-dimethylsilyl ligands it can be used to transfer phosphinidene to organic functional groups such as thioformaldehydes or diazenes, respectively. We propose that by exploiting the complex bonding nature of low-valent main group complexes they can act as synthetic equivalents of hitherto unknown very reactive synthons. We encourage experimentalists to explore the reactivity of their main-group complexes by varying the size of the bulky substituents on the reactants that can result in new unexpected chemistry.

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NHC‐stabilized Silicon(II) Halides: Reactivity Studies with Diazoalkanes and Azides

Abstract: Detailed studies of the reactivity of the NHC-stabilized (NHC = N-heterocyclic carbene) silicon(II)

Cited by 13 publications

References 128 publications

NHCs in Main Group Chemistry

NHCs in Main Group Chemistry

S–H Bond Activation in Hydrogen Sulfide by NHC-Stabilized Silyliumylidene Ions

Theoretical Evidence for the Utilization of Low‐Valent Main‐Group Complexes as Rare‐Synthon Equivalents

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