Novel silicon and phosphorus containing heterocycles

Hans H. Karsch; Roland Richter; Annette Schier; Maximilian Heckel; Robert Ficker; Wolfgang Hiller

doi:10.1016/0022-328X(95)05650-E

Novel silicon and phosphorus containing heterocycles

Hans H. Karsch
, Roland Richter
, Annette Schier
, Maximilian Heckel
, Robert Ficker
, Wolfgang Hiller

Natural Sciences

Technical University of Munich

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

13 Scopus citations

Abstract

The reactions of two or three equivalents of lithium phosphinomethanides with di- or trifunctional chlorosilanes yield novel five- and six-membered heterocycles with silicon and phosphorus ring members by multistep rearrangements and/or transmetallation reactions. Silaethene intermediates are likely to be involved. Three different types of reactions are described. 1. (1) RSiCl₃(a, R = Ph; b, R = Me; c, R = ^tBu) reacts with three equivalents of Li[C(PMe₂)₂(SiMe₃)] to give five-membered heterocycles (R)[(Me₃Si)C(PMe₂)₂]{A figure is presented}, 11, which are fluxional in solution. A PMe₂ group shift and transmetallation reaction are involved in their formation. 2. (2) PhSiCl₃ reacts with {Li[C(PMe₂)(SiMe₃)₂]}₂x TMEDA to give a five-membered heterocycle {A figure is presented}, via an intermediate mono- and disubstitution product. This reaction involves ligand rearrangement, elimination of Me₂PCl, and an, Me₃Si and Me group shift within a silaethene framework. 3. (3) Ph₂SiCl₂ reacts with two equivalents of Li[CH(PMe₂)₂] to give a six-membered heterocycle [Ph₂Si-C(PMe₂)=PMe₂^-]₂, 18, by transmetallation and LiCI elimination, possibly via a silaethene intermediate. X-ray analyses of lla, 17 and 18 confirm the proposed molecular structures based on nuclear magnetic resonance spectroscopy.

Original language	English
Pages (from-to)	167-177
Number of pages	11
Journal	Journal of Organometallic Chemistry
Volume	501
Issue number	1-2
DOIs	https://doi.org/10.1016/0022-328X(95)05650-E
State	Published - 4 Oct 1995

Keywords

Crystal structure
Phosphinomethanides
Phosphorus
Silaheterocycles
Silicon

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10.1016/0022-328X(95)05650-E

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@article{9f3388a544ec4219b78267fbddaa29f0,

title = "Novel silicon and phosphorus containing heterocycles",

abstract = "The reactions of two or three equivalents of lithium phosphinomethanides with di- or trifunctional chlorosilanes yield novel five- and six-membered heterocycles with silicon and phosphorus ring members by multistep rearrangements and/or transmetallation reactions. Silaethene intermediates are likely to be involved. Three different types of reactions are described. 1. (1) RSiCl3(a, R = Ph; b, R = Me; c, R = tBu) reacts with three equivalents of Li[C(PMe2)2(SiMe3)] to give five-membered heterocycles (R)[(Me3Si)C(PMe2)2]\{A figure is presented\}, 11, which are fluxional in solution. A PMe2 group shift and transmetallation reaction are involved in their formation. 2. (2) PhSiCl3 reacts with \{Li[C(PMe2)(SiMe3)2]\}2x TMEDA to give a five-membered heterocycle \{A figure is presented\}, via an intermediate mono- and disubstitution product. This reaction involves ligand rearrangement, elimination of Me2PCl, and an, Me3Si and Me group shift within a silaethene framework. 3. (3) Ph2SiCl2 reacts with two equivalents of Li[CH(PMe2)2] to give a six-membered heterocycle [Ph2Si-C(PMe2)=PMe2-]2, 18, by transmetallation and LiCI elimination, possibly via a silaethene intermediate. X-ray analyses of lla, 17 and 18 confirm the proposed molecular structures based on nuclear magnetic resonance spectroscopy.",

keywords = "Crystal structure, Phosphinomethanides, Phosphorus, Silaheterocycles, Silicon",

author = "Karsch, \{Hans H.\} and Roland Richter and Annette Schier and Maximilian Heckel and Robert Ficker and Wolfgang Hiller",

note = "Funding Information: and the Fonds der Chemischen Industrie for financial support. W.H. thanks Hewlett Packard for a fruitful cooperation. Funding Information: We thank Mr. J. Riede for X-ray data collection. H.H.K. thanks the Deutsche Forschungsgemeinschaft",

year = "1995",

month = oct,

day = "4",

doi = "10.1016/0022-328X(95)05650-E",

language = "English",

volume = "501",

pages = "167--177",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "1-2",

}

TY - JOUR

T1 - Novel silicon and phosphorus containing heterocycles

AU - Karsch, Hans H.

AU - Richter, Roland

AU - Schier, Annette

AU - Heckel, Maximilian

AU - Ficker, Robert

AU - Hiller, Wolfgang

N1 - Funding Information: and the Fonds der Chemischen Industrie for financial support. W.H. thanks Hewlett Packard for a fruitful cooperation. Funding Information: We thank Mr. J. Riede for X-ray data collection. H.H.K. thanks the Deutsche Forschungsgemeinschaft

PY - 1995/10/4

Y1 - 1995/10/4

N2 - The reactions of two or three equivalents of lithium phosphinomethanides with di- or trifunctional chlorosilanes yield novel five- and six-membered heterocycles with silicon and phosphorus ring members by multistep rearrangements and/or transmetallation reactions. Silaethene intermediates are likely to be involved. Three different types of reactions are described. 1. (1) RSiCl3(a, R = Ph; b, R = Me; c, R = tBu) reacts with three equivalents of Li[C(PMe2)2(SiMe3)] to give five-membered heterocycles (R)[(Me3Si)C(PMe2)2]{A figure is presented}, 11, which are fluxional in solution. A PMe2 group shift and transmetallation reaction are involved in their formation. 2. (2) PhSiCl3 reacts with {Li[C(PMe2)(SiMe3)2]}2x TMEDA to give a five-membered heterocycle {A figure is presented}, via an intermediate mono- and disubstitution product. This reaction involves ligand rearrangement, elimination of Me2PCl, and an, Me3Si and Me group shift within a silaethene framework. 3. (3) Ph2SiCl2 reacts with two equivalents of Li[CH(PMe2)2] to give a six-membered heterocycle [Ph2Si-C(PMe2)=PMe2-]2, 18, by transmetallation and LiCI elimination, possibly via a silaethene intermediate. X-ray analyses of lla, 17 and 18 confirm the proposed molecular structures based on nuclear magnetic resonance spectroscopy.

AB - The reactions of two or three equivalents of lithium phosphinomethanides with di- or trifunctional chlorosilanes yield novel five- and six-membered heterocycles with silicon and phosphorus ring members by multistep rearrangements and/or transmetallation reactions. Silaethene intermediates are likely to be involved. Three different types of reactions are described. 1. (1) RSiCl3(a, R = Ph; b, R = Me; c, R = tBu) reacts with three equivalents of Li[C(PMe2)2(SiMe3)] to give five-membered heterocycles (R)[(Me3Si)C(PMe2)2]{A figure is presented}, 11, which are fluxional in solution. A PMe2 group shift and transmetallation reaction are involved in their formation. 2. (2) PhSiCl3 reacts with {Li[C(PMe2)(SiMe3)2]}2x TMEDA to give a five-membered heterocycle {A figure is presented}, via an intermediate mono- and disubstitution product. This reaction involves ligand rearrangement, elimination of Me2PCl, and an, Me3Si and Me group shift within a silaethene framework. 3. (3) Ph2SiCl2 reacts with two equivalents of Li[CH(PMe2)2] to give a six-membered heterocycle [Ph2Si-C(PMe2)=PMe2-]2, 18, by transmetallation and LiCI elimination, possibly via a silaethene intermediate. X-ray analyses of lla, 17 and 18 confirm the proposed molecular structures based on nuclear magnetic resonance spectroscopy.

KW - Crystal structure

KW - Phosphinomethanides

KW - Phosphorus

KW - Silaheterocycles

KW - Silicon

UR - https://www.scopus.com/pages/publications/0007251866

U2 - 10.1016/0022-328X(95)05650-E

DO - 10.1016/0022-328X(95)05650-E

M3 - Article

AN - SCOPUS:0007251866

SN - 0022-328X

VL - 501

SP - 167

EP - 177

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -

Novel silicon and phosphorus containing heterocycles

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Keywords

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