Efficient Cobalt-Catalyzed Coupling of Amines and Siloxanes to Prepare Ceramics and Polymers

Anuja Sharma; Ren H. Bean; Timothy E. Long; Ryan J. Trovitch

doi:10.1021/acssuschemeng.3c01912

Efficient Cobalt-Catalyzed Coupling of Amines and Siloxanes to Prepare Ceramics and Polymers

Anuja Sharma, Ren H. Bean, Timothy E. Long, Ryan J. Trovitch

Molecular Sciences, School of (SMS)

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

5 Scopus citations

Abstract

The phosphine-substituted aryl diimine cobalt catalyst, (^Ph2PPrADI)Co, has been found to mediate the dehydrocoupling of diamines or polyamines to poly(methylhydrosiloxane) (PMHS) to generate hydrogen and crosslinked solids in an atom-efficient fashion. The resulting siloxane diamine and siloxane polyamine networks persist in the presence of air or water at room temperature and can tolerate temperatures of up to 1600 °C. Upon lowering the catalyst loading to 0.01 mol %, (^Ph2PPrADI)Co was found to catalyze the dehydrocoupling of 1,3-propanediamine and PMHS (m = 35) to generate a siloxane diamine foam with a turnover frequency of 157 s^-1 relative to diamine consumption, the highest activity ever reported for Si-N dehydrocoupling. Furthermore, upon systematically reducing the number of potential branch points, the (^Ph2PPrADI)Co-catalyzed dehydrocoupling of diamines with hydride-terminated poly(dimethylsiloxane) (PDMS) was found to yield linear siloxane diamine polymers with molecular weights of up to 47,300 g/mol.

Original language	English (US)
Pages (from-to)	11172-11180
Number of pages	9
Journal	ACS Sustainable Chemistry and Engineering
Volume	11
Issue number	30
DOIs	https://doi.org/10.1021/acssuschemeng.3c01912
State	Published - Jul 31 2023

Keywords

atom economy
catalysis
copolymers
earth-abundant metals
less hazardous synthesis
main group elements
waste prevention

ASJC Scopus subject areas

General Chemistry
Environmental Chemistry
General Chemical Engineering
Renewable Energy, Sustainability and the Environment

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10.1021/acssuschemeng.3c01912

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title = "Efficient Cobalt-Catalyzed Coupling of Amines and Siloxanes to Prepare Ceramics and Polymers",

abstract = "The phosphine-substituted aryl diimine cobalt catalyst, (Ph2PPrADI)Co, has been found to mediate the dehydrocoupling of diamines or polyamines to poly(methylhydrosiloxane) (PMHS) to generate hydrogen and crosslinked solids in an atom-efficient fashion. The resulting siloxane diamine and siloxane polyamine networks persist in the presence of air or water at room temperature and can tolerate temperatures of up to 1600 °C. Upon lowering the catalyst loading to 0.01 mol %, (Ph2PPrADI)Co was found to catalyze the dehydrocoupling of 1,3-propanediamine and PMHS (m = 35) to generate a siloxane diamine foam with a turnover frequency of 157 s-1 relative to diamine consumption, the highest activity ever reported for Si-N dehydrocoupling. Furthermore, upon systematically reducing the number of potential branch points, the (Ph2PPrADI)Co-catalyzed dehydrocoupling of diamines with hydride-terminated poly(dimethylsiloxane) (PDMS) was found to yield linear siloxane diamine polymers with molecular weights of up to 47,300 g/mol.",

keywords = "atom economy, catalysis, copolymers, earth-abundant metals, less hazardous synthesis, main group elements, waste prevention",

author = "Anuja Sharma and Bean, {Ren H.} and Long, {Timothy E.} and Trovitch, {Ryan J.}",

note = "Funding Information: This material is based upon work supported by the National Science Foundation under grant no. 2154359. Prof. Christina S. Birkel and Jordan Sinclair are acknowledged for assisting with powder X-ray diffraction analysis. We would also like to thank Prof. Richard M. Laine for helpful discussions. Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

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doi = "10.1021/acssuschemeng.3c01912",

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AU - Sharma, Anuja

AU - Bean, Ren H.

AU - Long, Timothy E.

AU - Trovitch, Ryan J.

N1 - Funding Information: This material is based upon work supported by the National Science Foundation under grant no. 2154359. Prof. Christina S. Birkel and Jordan Sinclair are acknowledged for assisting with powder X-ray diffraction analysis. We would also like to thank Prof. Richard M. Laine for helpful discussions. Publisher Copyright: © 2023 American Chemical Society.

PY - 2023/7/31

Y1 - 2023/7/31

N2 - The phosphine-substituted aryl diimine cobalt catalyst, (Ph2PPrADI)Co, has been found to mediate the dehydrocoupling of diamines or polyamines to poly(methylhydrosiloxane) (PMHS) to generate hydrogen and crosslinked solids in an atom-efficient fashion. The resulting siloxane diamine and siloxane polyamine networks persist in the presence of air or water at room temperature and can tolerate temperatures of up to 1600 °C. Upon lowering the catalyst loading to 0.01 mol %, (Ph2PPrADI)Co was found to catalyze the dehydrocoupling of 1,3-propanediamine and PMHS (m = 35) to generate a siloxane diamine foam with a turnover frequency of 157 s-1 relative to diamine consumption, the highest activity ever reported for Si-N dehydrocoupling. Furthermore, upon systematically reducing the number of potential branch points, the (Ph2PPrADI)Co-catalyzed dehydrocoupling of diamines with hydride-terminated poly(dimethylsiloxane) (PDMS) was found to yield linear siloxane diamine polymers with molecular weights of up to 47,300 g/mol.

AB - The phosphine-substituted aryl diimine cobalt catalyst, (Ph2PPrADI)Co, has been found to mediate the dehydrocoupling of diamines or polyamines to poly(methylhydrosiloxane) (PMHS) to generate hydrogen and crosslinked solids in an atom-efficient fashion. The resulting siloxane diamine and siloxane polyamine networks persist in the presence of air or water at room temperature and can tolerate temperatures of up to 1600 °C. Upon lowering the catalyst loading to 0.01 mol %, (Ph2PPrADI)Co was found to catalyze the dehydrocoupling of 1,3-propanediamine and PMHS (m = 35) to generate a siloxane diamine foam with a turnover frequency of 157 s-1 relative to diamine consumption, the highest activity ever reported for Si-N dehydrocoupling. Furthermore, upon systematically reducing the number of potential branch points, the (Ph2PPrADI)Co-catalyzed dehydrocoupling of diamines with hydride-terminated poly(dimethylsiloxane) (PDMS) was found to yield linear siloxane diamine polymers with molecular weights of up to 47,300 g/mol.

KW - atom economy

KW - catalysis

KW - copolymers

KW - earth-abundant metals

KW - less hazardous synthesis

KW - main group elements

KW - waste prevention

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Efficient Cobalt-Catalyzed Coupling of Amines and Siloxanes to Prepare Ceramics and Polymers

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Keywords

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