A Persistent 1,2-Dihydrophosphasilene Adduct

Kerstin Hansen; Tibor Szilvasi; Burgert Blom; Matthias Driess

doi:10.1002/anie.201508149

A Persistent 1,2-Dihydrophosphasilene Adduct

Kerstin Hansen
, Tibor Szilvasi
, Burgert Blom
, Matthias Driess^*

^*Corresponding author for this work

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

Abstract

The reaction of the arylchlorosilylene-NHC adduct ArSi(NHC)Cl [Ar = 2,6-Trip(2)-C6H3; NHC = (MeC)(2-)(NMe)(2)C] 1 with one molar equiv of LiPH2. dme (dme = 1,2dimethoxyethane) affords the first 1,2-dihydrophosphasilene adduct 2 (ArSi(NHC)(H)=PH). The latter is labile in solution and can undergo head-to-tail dimerization to give [ ArSi( H)PH](2) 3 and "free" NHC. Further stabilization of 2 by complexation with {W(CO)(5)} affords the isolable 1,2-dihydrophosphasilene- tungsten complex 4 [ArSi(NHC)(H)=P(H) W( CO) 5]. Additionally, the new 1-silyl-2-hydrophosphasilene ArSi(NHC)(H)=PSiMe3 5 could be synthesized and structurally characterized. DFT studies confirmed that the Si=P bond in 2 and 4 is mostly zwitterionic with drastically decreased double-bond character.

Original language	English
Pages (from-to)	15060-15063
Number of pages	4
Journal	Angewandte Chemie-International Edition
Volume	54
Issue number	50
DOIs	https://doi.org/10.1002/anie.201508149
Publication status	Published - 7 Dec 2015

Keywords

heavier olefin analogues
multiple bonds
phosphorus
silicon
zwitterions
HALF-PARENT PHOSPHASILENE
X-RAY-STRUCTURE
SILICON-PHOSPHORUS
ZWITTERIONIC PHOSPHASILENE
UNUSUAL REACTIVITY
DOUBLE-BONDS
SI-P
COMPLEXES
PHOSPHANES
CHEMISTRY

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10.1002/anie.201508149

CCDC 1421334 : Experimental Crystal Structure Determination
Hansen, K. (Creator), Szilvási, T. (Contributor), Blom, B. (Contributor) & Driess, M. (Contributor), Cambridge Crystallographic Data Centre, 29 Aug 2015
DOI: 10.5517/cc1jq0hr
Dataset/Software: Dataset
CCDC 1421335 : Experimental Crystal Structure Determination
Hansen, K. (Creator), Szilvási, T. (Contributor), Blom, B. (Contributor) & Driess, M. (Contributor), Cambridge Crystallographic Data Centre, 29 Aug 2015
DOI: 10.5517/cc1jq0js
Dataset/Software: Dataset

Cite this

@article{1e701e7fff654c1b89ba7c96a5a2c900,

title = "A Persistent 1,2-Dihydrophosphasilene Adduct",

abstract = "The reaction of the arylchlorosilylene-NHC adduct ArSi(NHC)Cl [Ar = 2,6-Trip(2)-C6H3; NHC = (MeC)(2-)(NMe)(2)C] 1 with one molar equiv of LiPH2. dme (dme = 1,2dimethoxyethane) affords the first 1,2-dihydrophosphasilene adduct 2 (ArSi(NHC)(H)=PH). The latter is labile in solution and can undergo head-to-tail dimerization to give [ ArSi( H)PH](2) 3 and {"}free{"} NHC. Further stabilization of 2 by complexation with \{W(CO)(5)\} affords the isolable 1,2-dihydrophosphasilene- tungsten complex 4 [ArSi(NHC)(H)=P(H) W( CO) 5]. Additionally, the new 1-silyl-2-hydrophosphasilene ArSi(NHC)(H)=PSiMe3 5 could be synthesized and structurally characterized. DFT studies confirmed that the Si=P bond in 2 and 4 is mostly zwitterionic with drastically decreased double-bond character.",

keywords = "heavier olefin analogues, multiple bonds, phosphorus, silicon, zwitterions, HALF-PARENT PHOSPHASILENE, X-RAY-STRUCTURE, SILICON-PHOSPHORUS, ZWITTERIONIC PHOSPHASILENE, UNUSUAL REACTIVITY, DOUBLE-BONDS, SI-P, COMPLEXES, PHOSPHANES, CHEMISTRY",

author = "Kerstin Hansen and Tibor Szilvasi and Burgert Blom and Matthias Driess",

year = "2015",

month = dec,

day = "7",

doi = "10.1002/anie.201508149",

language = "English",

volume = "54",

pages = "15060--15063",

journal = "Angewandte Chemie-International Edition",

issn = "1433-7851",

publisher = "John Wiley \& Sons Inc.",

number = "50",

}

TY - JOUR

T1 - A Persistent 1,2-Dihydrophosphasilene Adduct

AU - Hansen, Kerstin

AU - Szilvasi, Tibor

AU - Blom, Burgert

AU - Driess, Matthias

PY - 2015/12/7

Y1 - 2015/12/7

N2 - The reaction of the arylchlorosilylene-NHC adduct ArSi(NHC)Cl [Ar = 2,6-Trip(2)-C6H3; NHC = (MeC)(2-)(NMe)(2)C] 1 with one molar equiv of LiPH2. dme (dme = 1,2dimethoxyethane) affords the first 1,2-dihydrophosphasilene adduct 2 (ArSi(NHC)(H)=PH). The latter is labile in solution and can undergo head-to-tail dimerization to give [ ArSi( H)PH](2) 3 and "free" NHC. Further stabilization of 2 by complexation with {W(CO)(5)} affords the isolable 1,2-dihydrophosphasilene- tungsten complex 4 [ArSi(NHC)(H)=P(H) W( CO) 5]. Additionally, the new 1-silyl-2-hydrophosphasilene ArSi(NHC)(H)=PSiMe3 5 could be synthesized and structurally characterized. DFT studies confirmed that the Si=P bond in 2 and 4 is mostly zwitterionic with drastically decreased double-bond character.

AB - The reaction of the arylchlorosilylene-NHC adduct ArSi(NHC)Cl [Ar = 2,6-Trip(2)-C6H3; NHC = (MeC)(2-)(NMe)(2)C] 1 with one molar equiv of LiPH2. dme (dme = 1,2dimethoxyethane) affords the first 1,2-dihydrophosphasilene adduct 2 (ArSi(NHC)(H)=PH). The latter is labile in solution and can undergo head-to-tail dimerization to give [ ArSi( H)PH](2) 3 and "free" NHC. Further stabilization of 2 by complexation with {W(CO)(5)} affords the isolable 1,2-dihydrophosphasilene- tungsten complex 4 [ArSi(NHC)(H)=P(H) W( CO) 5]. Additionally, the new 1-silyl-2-hydrophosphasilene ArSi(NHC)(H)=PSiMe3 5 could be synthesized and structurally characterized. DFT studies confirmed that the Si=P bond in 2 and 4 is mostly zwitterionic with drastically decreased double-bond character.

KW - heavier olefin analogues

KW - multiple bonds

KW - phosphorus

KW - silicon

KW - zwitterions

KW - HALF-PARENT PHOSPHASILENE

KW - X-RAY-STRUCTURE

KW - SILICON-PHOSPHORUS

KW - ZWITTERIONIC PHOSPHASILENE

KW - UNUSUAL REACTIVITY

KW - DOUBLE-BONDS

KW - SI-P

KW - COMPLEXES

KW - PHOSPHANES

KW - CHEMISTRY

U2 - 10.1002/anie.201508149

DO - 10.1002/anie.201508149

M3 - Article

SN - 1433-7851

VL - 54

SP - 15060

EP - 15063

JO - Angewandte Chemie-International Edition

JF - Angewandte Chemie-International Edition

IS - 50

ER -

A Persistent 1,2-Dihydrophosphasilene Adduct

Abstract

Keywords

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Datasets

CCDC 1421334 : Experimental Crystal Structure Determination

CCDC 1421335 : Experimental Crystal Structure Determination

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