Silicon and Phosphinomethanides: Novel Heteroelement Substituted Methanes and Ylides

Hans Heinz Karsch; Roland Richter

doi:10.1002/9783527620777.ch24a

Silicon and Phosphinomethanides: Novel Heteroelement Substituted Methanes and Ylides

Hans Heinz Karsch
, Roland Richter

Natural Sciences

Technical University of Munich

Research output: Chapter in Book/Report/Conference proceeding › Chapter › peer-review

Abstract

LiCH(PMe₂)₂ reacts with SiC1₄ or with PhR₂SiCl (R = Me, Ph) via the carbanion to give silyl substituted phosphinomethanes. HC(PMe₂)₂(SiMe₂Ph) is deprotonated by nBuLi to give trimeric Li[C(PMe₂),(SiMe₂Ph)]₃. Li[C(PMe₂)₂(SiMe₂),]₃.TMEDA 3 reacts with RR'SiCl₂, via both the carbanion, thus generating a tetraheteroatom substituted methane moiety and, in a second substitution step, via phosphorus, thus forming an ylidic moiety. This proposed reaction pathway can be verified by the reaction of PhSiC1₃ with a half equivalent of 3 where "C"-coordination of the ligand is obtained. Novel skeletal rearrangements and C-H activation reactions starting from RSiCl, (R = Ph, tBu, Me) under formation of fivemembered heterocycles are reported.

Original language	English
Title of host publication	Organosilicon Chemistry Set
Subtitle of host publication	From Molecules to Materials
Publisher	wiley
Pages	187-193
Number of pages	7
ISBN (Electronic)	9783527620777
ISBN (Print)	9783527323470
DOIs	https://doi.org/10.1002/9783527620777.ch24a
State	Published - 10 Jun 2008

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title = "Silicon and Phosphinomethanides: Novel Heteroelement Substituted Methanes and Ylides",

abstract = "LiCH(PMe2)2 reacts with SiC14 or with PhR2SiCl (R = Me, Ph) via the carbanion to give silyl substituted phosphinomethanes. HC(PMe2)2(SiMe2Ph) is deprotonated by nBuLi to give trimeric Li[C(PMe2),(SiMe2Ph)]3. Li[C(PMe2)2(SiMe2),]3.TMEDA 3 reacts with RR'SiCl2, via both the carbanion, thus generating a tetraheteroatom substituted methane moiety and, in a second substitution step, via phosphorus, thus forming an ylidic moiety. This proposed reaction pathway can be verified by the reaction of PhSiC13 with a half equivalent of 3 where {"}C{"}-coordination of the ligand is obtained. Novel skeletal rearrangements and C-H activation reactions starting from RSiCl, (R = Ph, tBu, Me) under formation of fivemembered heterocycles are reported.",

author = "Karsch, \{Hans Heinz\} and Roland Richter",

year = "2008",

month = jun,

day = "10",

doi = "10.1002/9783527620777.ch24a",

language = "English",

isbn = "9783527323470",

pages = "187--193",

booktitle = "Organosilicon Chemistry Set",

publisher = "wiley",

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TY - CHAP

T1 - Silicon and Phosphinomethanides

T2 - Novel Heteroelement Substituted Methanes and Ylides

AU - Karsch, Hans Heinz

AU - Richter, Roland

PY - 2008/6/10

Y1 - 2008/6/10

N2 - LiCH(PMe2)2 reacts with SiC14 or with PhR2SiCl (R = Me, Ph) via the carbanion to give silyl substituted phosphinomethanes. HC(PMe2)2(SiMe2Ph) is deprotonated by nBuLi to give trimeric Li[C(PMe2),(SiMe2Ph)]3. Li[C(PMe2)2(SiMe2),]3.TMEDA 3 reacts with RR'SiCl2, via both the carbanion, thus generating a tetraheteroatom substituted methane moiety and, in a second substitution step, via phosphorus, thus forming an ylidic moiety. This proposed reaction pathway can be verified by the reaction of PhSiC13 with a half equivalent of 3 where "C"-coordination of the ligand is obtained. Novel skeletal rearrangements and C-H activation reactions starting from RSiCl, (R = Ph, tBu, Me) under formation of fivemembered heterocycles are reported.

AB - LiCH(PMe2)2 reacts with SiC14 or with PhR2SiCl (R = Me, Ph) via the carbanion to give silyl substituted phosphinomethanes. HC(PMe2)2(SiMe2Ph) is deprotonated by nBuLi to give trimeric Li[C(PMe2),(SiMe2Ph)]3. Li[C(PMe2)2(SiMe2),]3.TMEDA 3 reacts with RR'SiCl2, via both the carbanion, thus generating a tetraheteroatom substituted methane moiety and, in a second substitution step, via phosphorus, thus forming an ylidic moiety. This proposed reaction pathway can be verified by the reaction of PhSiC13 with a half equivalent of 3 where "C"-coordination of the ligand is obtained. Novel skeletal rearrangements and C-H activation reactions starting from RSiCl, (R = Ph, tBu, Me) under formation of fivemembered heterocycles are reported.

UR - https://www.scopus.com/pages/publications/84959092149

U2 - 10.1002/9783527620777.ch24a

DO - 10.1002/9783527620777.ch24a

M3 - Chapter

AN - SCOPUS:84959092149

SN - 9783527323470

SP - 187

EP - 193

BT - Organosilicon Chemistry Set

PB - wiley

ER -

Silicon and Phosphinomethanides: Novel Heteroelement Substituted Methanes and Ylides

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