Cyclo-oligomerization of isocyanates with Na(PH[sub]2) or Na(OCP) as "P-" anion sources

Dominikus Heift; Zoltán Benko; Hansjörg Grützmacher; Andrew R. Jupp; Jose M. Goicoechea

doi:10.1039/C5SC00963D

Cyclo-oligomerization of isocyanates with Na(PH[sub]2) or Na(OCP) as "P-" anion sources

Dominikus Heift
, Zoltán Benko
, Hansjörg Grützmacher
, Andrew R. Jupp
, Jose M. Goicoechea

Swiss Federal Institute of Technology Zurich
Budapest University of Technology and Economics
Sun Yat-Sen University
University of Oxford

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

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Abstract

We show that the 2-phosphaethynolate anion, OCP-, is a simple and efficient catalyst for the cyclotrimerization of isocyanates. This process proceeds step-wise and involves five-membered heterocycles, namely 1,4,2-diazaphospholidine-3,5-dionide anions and spiro-phosphoranides as detectable intermediates, both of which were also found to be involved in the catalytic conversion. These species can be considered as adducts of a phosphide anion with two and four isocyanate molecules, respectively, demonstrating that the OCP- anion acts as a formal ‟P-” source. The interconversion between these anionic species was found to be reversible, allowing them to serve as reservoirs for unique phosphorus-based living-catalysts for isocyanate trimerization.

Original language	English
Pages (from-to)	4017-4024
Journal	Chemical Science
Volume	6
Issue number	7
Early online date	13 May 2015
DOIs	https://doi.org/10.1039/C5SC00963D
Publication status	Published - 1 Jul 2015

Bibliographical note

Note: This work was supported by the Swiss National Science Foundation (SNF), the ETH Zurich, and Sun Yat-Sen University. The János Bolyai Research Fellowship (for Z.B.), the EPSRC and the University of Oxford (DTA studentship A.R.J.) are gratefully acknowledged.

Keywords

Chemistry

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10.1039/C5SC00963D

Heift-D-47204-VoRFinal published version, 1.08 MBLicence: CC BY-NC

https://doi.org/10.1039/C5SC00963D

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@article{6fae24ec78934211aa66fac21089e2a1,

title = "Cyclo-oligomerization of isocyanates with Na(PH[sub]2) or Na(OCP) as {"}P-{"} anion sources",

abstract = "We show that the 2-phosphaethynolate anion, OCP-, is a simple and efficient catalyst for the cyclotrimerization of isocyanates. This process proceeds step-wise and involves five-membered heterocycles, namely 1,4,2-diazaphospholidine-3,5-dionide anions and spiro-phosphoranides as detectable intermediates, both of which were also found to be involved in the catalytic conversion. These species can be considered as adducts of a phosphide anion with two and four isocyanate molecules, respectively, demonstrating that the OCP- anion acts as a formal ‟P-” source. The interconversion between these anionic species was found to be reversible, allowing them to serve as reservoirs for unique phosphorus-based living-catalysts for isocyanate trimerization.",

keywords = "Chemistry",

author = "Dominikus Heift and Zolt{\'a}n Benko and Hansj{\"o}rg Gr{\"u}tzmacher and Jupp, \{Andrew R.\} and Goicoechea, \{Jose M.\}",

note = "Note: This work was supported by the Swiss National Science Foundation (SNF), the ETH Zurich, and Sun Yat-Sen University. The J{\'a}nos Bolyai Research Fellowship (for Z.B.), the EPSRC and the University of Oxford (DTA studentship A.R.J.) are gratefully acknowledged.",

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doi = "10.1039/C5SC00963D",

language = "English",

volume = "6",

pages = "4017--4024",

journal = "Chemical Science",

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T1 - Cyclo-oligomerization of isocyanates with Na(PH[sub]2) or Na(OCP) as "P-" anion sources

AU - Heift, Dominikus

AU - Benko, Zoltán

AU - Grützmacher, Hansjörg

AU - Jupp, Andrew R.

AU - Goicoechea, Jose M.

N1 - Note: This work was supported by the Swiss National Science Foundation (SNF), the ETH Zurich, and Sun Yat-Sen University. The János Bolyai Research Fellowship (for Z.B.), the EPSRC and the University of Oxford (DTA studentship A.R.J.) are gratefully acknowledged.

PY - 2015/7/1

Y1 - 2015/7/1

N2 - We show that the 2-phosphaethynolate anion, OCP-, is a simple and efficient catalyst for the cyclotrimerization of isocyanates. This process proceeds step-wise and involves five-membered heterocycles, namely 1,4,2-diazaphospholidine-3,5-dionide anions and spiro-phosphoranides as detectable intermediates, both of which were also found to be involved in the catalytic conversion. These species can be considered as adducts of a phosphide anion with two and four isocyanate molecules, respectively, demonstrating that the OCP- anion acts as a formal ‟P-” source. The interconversion between these anionic species was found to be reversible, allowing them to serve as reservoirs for unique phosphorus-based living-catalysts for isocyanate trimerization.

AB - We show that the 2-phosphaethynolate anion, OCP-, is a simple and efficient catalyst for the cyclotrimerization of isocyanates. This process proceeds step-wise and involves five-membered heterocycles, namely 1,4,2-diazaphospholidine-3,5-dionide anions and spiro-phosphoranides as detectable intermediates, both of which were also found to be involved in the catalytic conversion. These species can be considered as adducts of a phosphide anion with two and four isocyanate molecules, respectively, demonstrating that the OCP- anion acts as a formal ‟P-” source. The interconversion between these anionic species was found to be reversible, allowing them to serve as reservoirs for unique phosphorus-based living-catalysts for isocyanate trimerization.

KW - Chemistry

U2 - 10.1039/C5SC00963D

DO - 10.1039/C5SC00963D

M3 - Article

SN - 2041-6520

VL - 6

SP - 4017

EP - 4024

JO - Chemical Science

JF - Chemical Science

IS - 7

ER -

Cyclo-oligomerization of isocyanates with Na(PH[sub]2) or Na(OCP) as "P-" anion sources

Abstract

Bibliographical note

Keywords

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