An ylide-like phosphasilene and striking formation of a 4π-electron, resonance-stabilized 2,4-disila-1,3-diphosphacyclobutadiene

Shigeyoshi Inoue; Wenyuan Wang; Carsten Präsang; Matthew Asay; Elisabeth Irran; Matthias Driess

doi:10.1021/ja200462y

An ylide-like phosphasilene and striking formation of a 4π-electron, resonance-stabilized 2,4-disila-1,3-diphosphacyclobutadiene

Shigeyoshi Inoue
, Wenyuan Wang
, Carsten Präsang
, Matthew Asay
, Elisabeth Irran
, Matthias Driess

Technische Universität Berlin

Research output: Contribution to journal › Article › peer-review

110 Scopus citations

Abstract

The first N-donor-stabilized phosphasilene LSi(SiMe₃)=PSiMe ₃ (L = PhC(NtBu)₂) has been synthesized in 87% yield through 1,2-silyl migration of the (Me₃Si)₂P-substituted, N-heterocyclic silylene [LSi-P(SiMe₃)₂]. Remarkably, the latter reacts with dichlorotriphenylphosphorane Ph₃PCl₂ to give the unprecedented 4π-electron Si₂P₂- cycloheterobutadiene [(LSi)₂P₂] with two-coordinate phosphorus atoms. The striking molecular structures as well as the ²⁹Si and ³¹P NMR spectroscopic features of both products indicate the presence of zwitterionic Si=P bonds which is also in accordance with results by DFT calculations.

Original language	English
Pages (from-to)	2868-2871
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	133
Issue number	9
DOIs	https://doi.org/10.1021/ja200462y
State	Published - 9 Mar 2011
Externally published	Yes

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title = "An ylide-like phosphasilene and striking formation of a 4π-electron, resonance-stabilized 2,4-disila-1,3-diphosphacyclobutadiene",

abstract = "The first N-donor-stabilized phosphasilene LSi(SiMe3)=PSiMe 3 (L = PhC(NtBu)2) has been synthesized in 87\% yield through 1,2-silyl migration of the (Me3Si)2P-substituted, N-heterocyclic silylene [LSi-P(SiMe3)2]. Remarkably, the latter reacts with dichlorotriphenylphosphorane Ph3PCl2 to give the unprecedented 4π-electron Si2P2- cycloheterobutadiene [(LSi)2P2] with two-coordinate phosphorus atoms. The striking molecular structures as well as the 29Si and 31P NMR spectroscopic features of both products indicate the presence of zwitterionic Si=P bonds which is also in accordance with results by DFT calculations.",

author = "Shigeyoshi Inoue and Wenyuan Wang and Carsten Pr{\"a}sang and Matthew Asay and Elisabeth Irran and Matthias Driess",

year = "2011",

month = mar,

day = "9",

doi = "10.1021/ja200462y",

language = "English",

volume = "133",

pages = "2868--2871",

journal = "Journal of the American Chemical Society",

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T1 - An ylide-like phosphasilene and striking formation of a 4π-electron, resonance-stabilized 2,4-disila-1,3-diphosphacyclobutadiene

AU - Inoue, Shigeyoshi

AU - Wang, Wenyuan

AU - Präsang, Carsten

AU - Asay, Matthew

AU - Irran, Elisabeth

AU - Driess, Matthias

PY - 2011/3/9

Y1 - 2011/3/9

N2 - The first N-donor-stabilized phosphasilene LSi(SiMe3)=PSiMe 3 (L = PhC(NtBu)2) has been synthesized in 87% yield through 1,2-silyl migration of the (Me3Si)2P-substituted, N-heterocyclic silylene [LSi-P(SiMe3)2]. Remarkably, the latter reacts with dichlorotriphenylphosphorane Ph3PCl2 to give the unprecedented 4π-electron Si2P2- cycloheterobutadiene [(LSi)2P2] with two-coordinate phosphorus atoms. The striking molecular structures as well as the 29Si and 31P NMR spectroscopic features of both products indicate the presence of zwitterionic Si=P bonds which is also in accordance with results by DFT calculations.

AB - The first N-donor-stabilized phosphasilene LSi(SiMe3)=PSiMe 3 (L = PhC(NtBu)2) has been synthesized in 87% yield through 1,2-silyl migration of the (Me3Si)2P-substituted, N-heterocyclic silylene [LSi-P(SiMe3)2]. Remarkably, the latter reacts with dichlorotriphenylphosphorane Ph3PCl2 to give the unprecedented 4π-electron Si2P2- cycloheterobutadiene [(LSi)2P2] with two-coordinate phosphorus atoms. The striking molecular structures as well as the 29Si and 31P NMR spectroscopic features of both products indicate the presence of zwitterionic Si=P bonds which is also in accordance with results by DFT calculations.

UR - https://www.scopus.com/pages/publications/79952271210

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DO - 10.1021/ja200462y

M3 - Article

AN - SCOPUS:79952271210

SN - 0002-7863

VL - 133

SP - 2868

EP - 2871

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 9

ER -

An ylide-like phosphasilene and striking formation of a 4π-electron, resonance-stabilized 2,4-disila-1,3-diphosphacyclobutadiene

Abstract

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