Phosphide Delivery to a Cyclotrisilene

Thomas P. Robinson; Michael J. Cowley; David Scheschkewitz; Jose M. Goicoechea

doi:10.1002/anie.201409908

Phosphide Delivery to a Cyclotrisilene

Thomas P. Robinson, Michael J. Cowley, David Scheschkewitz^*, Jose M. Goicoechea

^*Corresponding author for this work

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

Abstract

The reactivity of the 2-phosphaethynolate anion (PCO^-) towards a cyclic trisilene (cSi₃(Tip)₄) is reported. The result is the net activation of the P—C and Si—Si multiple bonds of the precursors affording a heteroatomic bicyclo[1.1.1]pentan-2-one analogue ([P(CO)Si-₃(Tip)₄]^-; 1). This reaction can be interpreted as the formal addition of a phosphide and a carbonyl across the Si—Si double bond. Photolytic decarbonylation of 1 results in the incorporation of the phosphide vertex into the cyclotrisilene scaffold, yielding a congener of the cyclobutene anion with considerable allylic character.

Original language	English
Pages (from-to)	683-686
Number of pages	4
Journal	Angewandte Chemie International Edition
Volume	54
Issue number	2
Early online date	21 Nov 2014
DOIs	https://doi.org/10.1002/anie.201409908
Publication status	Published - 7 Jan 2015

Keywords

2-phosphaethynolate
main-group chemistry
multiple bonds
silenes
silicon
HALF-PARENT PHOSPHASILENE
SODIUM PHOSPHAETHYNOLATE
CHEMICAL-SHIFTS
COVALENT RADII
SILICON
PHOSPHORUS
DISILENES
CONJUGATION
METALATION
CHEMISTRY

Access to Document

10.1002/anie.201409908

Phosphide Delivery to a Cyclotrisilene
Copyright © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Final published version, 429 KBLicence: Creative Commons: Attribution (CC-BY)

http://onlinelibrary.wiley.com/doi/10.1002/anie.201409908/full

Cite this

@article{ca0cdeee11684b698868360285ba2197,

title = "Phosphide Delivery to a Cyclotrisilene",

abstract = "The reactivity of the 2-phosphaethynolate anion (PCO-) towards a cyclic trisilene (cSi3(Tip)4) is reported. The result is the net activation of the P—C and Si—Si multiple bonds of the precursors affording a heteroatomic bicyclo[1.1.1]pentan-2-one analogue ([P(CO)Si-3(Tip)4]-; 1). This reaction can be interpreted as the formal addition of a phosphide and a carbonyl across the Si—Si double bond. Photolytic decarbonylation of 1 results in the incorporation of the phosphide vertex into the cyclotrisilene scaffold, yielding a congener of the cyclobutene anion with considerable allylic character.",

keywords = "2-phosphaethynolate, main-group chemistry, multiple bonds, silenes, silicon, HALF-PARENT PHOSPHASILENE, SODIUM PHOSPHAETHYNOLATE, CHEMICAL-SHIFTS, COVALENT RADII, SILICON, PHOSPHORUS, DISILENES, CONJUGATION, METALATION, CHEMISTRY",

author = "Robinson, {Thomas P.} and Cowley, {Michael J.} and David Scheschkewitz and Goicoechea, {Jose M.}",

year = "2015",

month = jan,

day = "7",

doi = "10.1002/anie.201409908",

language = "English",

volume = "54",

pages = "683--686",

journal = "Angewandte Chemie International Edition",

issn = "1433-7851",

publisher = "WILEY-V C H VERLAG GMBH",

number = "2",

}

TY - JOUR

T1 - Phosphide Delivery to a Cyclotrisilene

AU - Robinson, Thomas P.

AU - Cowley, Michael J.

AU - Scheschkewitz, David

AU - Goicoechea, Jose M.

PY - 2015/1/7

Y1 - 2015/1/7

N2 - The reactivity of the 2-phosphaethynolate anion (PCO-) towards a cyclic trisilene (cSi3(Tip)4) is reported. The result is the net activation of the P—C and Si—Si multiple bonds of the precursors affording a heteroatomic bicyclo[1.1.1]pentan-2-one analogue ([P(CO)Si-3(Tip)4]-; 1). This reaction can be interpreted as the formal addition of a phosphide and a carbonyl across the Si—Si double bond. Photolytic decarbonylation of 1 results in the incorporation of the phosphide vertex into the cyclotrisilene scaffold, yielding a congener of the cyclobutene anion with considerable allylic character.

AB - The reactivity of the 2-phosphaethynolate anion (PCO-) towards a cyclic trisilene (cSi3(Tip)4) is reported. The result is the net activation of the P—C and Si—Si multiple bonds of the precursors affording a heteroatomic bicyclo[1.1.1]pentan-2-one analogue ([P(CO)Si-3(Tip)4]-; 1). This reaction can be interpreted as the formal addition of a phosphide and a carbonyl across the Si—Si double bond. Photolytic decarbonylation of 1 results in the incorporation of the phosphide vertex into the cyclotrisilene scaffold, yielding a congener of the cyclobutene anion with considerable allylic character.

KW - 2-phosphaethynolate

KW - main-group chemistry

KW - multiple bonds

KW - silenes

KW - silicon

KW - HALF-PARENT PHOSPHASILENE

KW - SODIUM PHOSPHAETHYNOLATE

KW - CHEMICAL-SHIFTS

KW - COVALENT RADII

KW - SILICON

KW - PHOSPHORUS

KW - DISILENES

KW - CONJUGATION

KW - METALATION

KW - CHEMISTRY

U2 - 10.1002/anie.201409908

DO - 10.1002/anie.201409908

M3 - Article

VL - 54

SP - 683

EP - 686

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

SN - 1433-7851

IS - 2

ER -