Systematic synthesis in the polysilane series

Urry, Grant

doi:10.1021/ar50033a004

Cited by 73 publications

(25 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Tentative suggestions for the base‐induced disproportionation mechanism adapted from the literature are compiled in Scheme and include i) concerted silylene extrusion/insertion, ii) a metathesis‐like, concerted four‐center exchange of Cl for SiCl 3 in a primary amine adduct of Si 2 Cl 6 , or iii) heterolytic Si–Si bond cleavage followed by Cl/NR 3 exchange as key elementary steps . Support for the commonly accepted role of dichlorosilylene as a key intermediate in these reactions was only recently provided. In 2011, Roesky and co‐workers were able to characterize a SiCl 2 ⋅ NHC adduct by means of X‐ray analysis .…”

Section: Introductionmentioning

confidence: 99%

Unraveling the Amine‐Induced Disproportionation Reaction of Perchlorinated Silanes—A DFT Study

Schweizer

Meyer

Nadj

et al. 2016

Chemistry A European J

View full text Add to dashboard Cite

A detailed quantum-chemical study on the amine-induced disproportionation reaction of perchlorinated silanes to neo-Si5 Cl12 is reported. The key intermediate in the resulting mechanistic scenario is a dichlorosilylene amine adduct, which is in tune with recent experimental findings. Yet, at variance with the generally accepted notion of silicon-chain growth by concerted silylene insertion into Si-Cl bonds of lower silanes, the formation of neo-Si5 Cl12 follows more complex pathways. The reactivity is dominated by the Lewis-base character of the dichlorosilylene amine adduct and characterized by three elementary steps that bear close resemblance to the key elementary steps identified earlier for the chloride-induced disproportionation of Si2 Cl6 . NBO and QTAIM analyses of the key reactive species SiCl2 ⋅NMe3 and SiCl3 (-) provide a rationale for these striking similarities.

show abstract

Section: Introductionmentioning

confidence: 99%

Unraveling the Amine‐Induced Disproportionation Reaction of Perchlorinated Silanes—A DFT Study

Schweizer

Meyer

Nadj

et al. 2016

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Are structures II formed by SiCl 2 insertion into the P–Cl bond, or by substitutive Cl – /SiCl 3 – exchange, and how are the unsymmetric dimers formed? Related reaction paths (SiCl 2 insertion vs. Cl – /SiCl 3 – exchange) have been discussed since Urry studied the classic amine‐catalyzed disproportionation of Si 2 Cl 6 yielding Si(SiCl 3 ) 4 and SiCl 4 several decades ago.…”

Section: Introductionmentioning

confidence: 99%

Dichlorosilylene Transfer to a P‐Fluorophosphaalkene: The Route to a C‐Dichlorofluorosilyl‐Functionalized Dialkyldiphosphene

et al. 2017

View full text Add to dashboard Cite

Reactions of the (trichlorosilyl)germane Me3GeSiCl3 and of the unsymmetric disilane Me3SiSiCl3 with the P‐fluorophosphaalkene (Me3Si)2C=PF (1) proceed with transfer of SiCl2 (2) leading to the new C‐dichlorofluorosilyl‐functionalized dialkyldiphosphene (Cl2FSi)(Me3Si)2CP=PC(SiCl2F)(SiMe3)2 (6), which was characterized by X‐ray crystallography. The P‐phosphanylphosphaalkene (Me3Si)2C=PP[C(SiCl2F)(SiMe3)2]SiCl2F (8a) was detected in the reaction mixtures by 31P NMR spectroscopy, accompanied by its isomer 8b, presumably (Cl2FSi)(Me3Si)C=PP[C(SiCl2F)(SiMe3)2]SiMe3. The unsymmetric dimers 8a and 8b rearrange by a 1,3‐(P→C) silyl group shift, providing the inversion‐symmetric diphosphene 6. Compound 6 was transformed with selenium into a selenadiphosphirane (9). Quantum chemical calculations were performed on intermediates on the route from 1 and 2 to the metastable unsymmetric dimers 8a and 8b. The addition of SiCl2 to the P=C bond of 1, followed by ring opening of the silaphosphirane 4, provides the phosphinidene (Me3Si)2(Cl2FSi)CP (5), which rearranges further to isomeric P‐silylphosphaalkenes (Me3Si)2C=PSiCl2F (7a) and (Cl2FSi)(Me3Si)C=PSiMe3 (7b). Rapid phosphinidene–phosphaalkene P–P coupling reactions of 5 with 7a and with 7b followed by 1,2‐(P→P) silyl group shift of ylide‐type dimers 11a and 11b explain the formation of the observed species 8a and 8b. The absence of species related to 8b in previous experiments on the reactions of the P‐chlorophosphaalkene (Me3Si)2C=PCl (1′) with Si2Cl6, with Me3GeSiCl3, and with Me3SiSiCl3, allows us to suggest that in the P‐chlorophosphaalkene case nucleophile‐supported SiCl2 insertion into the P–Cl bond or the substitutive Cl–/SiCl3– exchange are the preferred routes to the metastable P‐(trichlorosilyl)phosphaalkene (Me3Si)2C=PSiCl3.

show abstract

“…Continuing with the theme of low-coordinate silicon chemistry, the study of Si(II) dihalides in the gas phase and under cryogenic conditions [46] has industrial relevance given the likely presence of SiF 2 during the plasma etching of elemental silicon [47] and the role of transient SiCl 2 during the high temperature synthesis of high purity silicon via the reaction of HSiCl 3 with H 2 [48]. Unfortunately attempts to isolate pure SiX 2 species results in either oligomerization or disproportionation to give SiX 4 and silicon metal.…”

Section: Trapping Silicon(ii) Halides and Hydrides In The Form Of Stamentioning

confidence: 99%

Recent Advances in the N-Heterocyclic Carbene-Supported Chemistry of Silicon

Rivard

2013

Functional Molecular Silicon Compounds II

View full text Add to dashboard Cite

show abstract

Systematic synthesis in the polysilane series

Cited by 73 publications

References 20 publications

Unraveling the Amine‐Induced Disproportionation Reaction of Perchlorinated Silanes—A DFT Study

Unraveling the Amine‐Induced Disproportionation Reaction of Perchlorinated Silanes—A DFT Study

Dichlorosilylene Transfer to a P‐Fluorophosphaalkene: The Route to a C‐Dichlorofluorosilyl‐Functionalized Dialkyldiphosphene

Recent Advances in the N-Heterocyclic Carbene-Supported Chemistry of Silicon

Contact Info

Product

Resources

About