Iron-mediated coupling of carbon dioxide and ethylene: Macrocyclic metallalactones enable access to various carboxylates

Stephan M. Rummelt; Hongyu Zhong; Ilia Korobkov; Paul J. Chirik

doi:10.1021/jacs.8b07558

Iron-mediated coupling of carbon dioxide and ethylene: Macrocyclic metallalactones enable access to various carboxylates

Stephan M. Rummelt
, Hongyu Zhong
, Ilia Korobkov
, Paul J. Chirik

Chemistry

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

44 Scopus citations

Abstract

Treatment of (^iPrPDI)Fe(N₂)₂ (^iPrPDI, 2,6-(2,6-iPr₂C₆H₃Nâ• CMe)₂C₅H₃N) with CO₂ and ethylene resulted in the formation of a homologous series of saturated and unsaturated iron carboxylate products, (^iPrPDI)Fe(O₂CR), the distribution of which depends on the ratio of the reagents. The solid-state and electronic structures of a saturated product, (^iPrPDI)Fe(O₂CC₂H₅), were elucidated. Product distributions, deuterium labeling studies, and stoichiometric experiments support initial formation of a five-membered metallalactone intermediate, which undergoes subsequent ethylene insertions to generate macrocyclic metallalactones. Competitive β-hydride elimination, CO₂ insertion, or reaction with H₂ determines the fate of the metallalactone, the latter accounting for formation of iron complexes with saturated carboxylates. Similar reactivity was observed upon addition of propiolactone and ethylene to (^iPrPDI)Fe(N₂)₂, supporting C-O oxidative addition and C-C bond formation through metallacycle intermediates.

Original language	English (US)
Pages (from-to)	11589-11593
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	140
Issue number	37
DOIs	https://doi.org/10.1021/jacs.8b07558
State	Published - Sep 19 2018

All Science Journal Classification (ASJC) codes

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

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@article{84855b96b18c4aceae3a7f69b588b4c1,

title = "Iron-mediated coupling of carbon dioxide and ethylene: Macrocyclic metallalactones enable access to various carboxylates",

abstract = "Treatment of (iPrPDI)Fe(N2)2 (iPrPDI, 2,6-(2,6-iPr2C6H3N{\^a}• CMe)2C5H3N) with CO2 and ethylene resulted in the formation of a homologous series of saturated and unsaturated iron carboxylate products, (iPrPDI)Fe(O2CR), the distribution of which depends on the ratio of the reagents. The solid-state and electronic structures of a saturated product, (iPrPDI)Fe(O2CC2H5), were elucidated. Product distributions, deuterium labeling studies, and stoichiometric experiments support initial formation of a five-membered metallalactone intermediate, which undergoes subsequent ethylene insertions to generate macrocyclic metallalactones. Competitive β-hydride elimination, CO2 insertion, or reaction with H2 determines the fate of the metallalactone, the latter accounting for formation of iron complexes with saturated carboxylates. Similar reactivity was observed upon addition of propiolactone and ethylene to (iPrPDI)Fe(N2)2, supporting C-O oxidative addition and C-C bond formation through metallacycle intermediates.",

author = "Rummelt, \{Stephan M.\} and Hongyu Zhong and Ilia Korobkov and Chirik, \{Paul J.\}",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = sep,

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doi = "10.1021/jacs.8b07558",

language = "English (US)",

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T1 - Iron-mediated coupling of carbon dioxide and ethylene

T2 - Macrocyclic metallalactones enable access to various carboxylates

AU - Rummelt, Stephan M.

AU - Zhong, Hongyu

AU - Korobkov, Ilia

AU - Chirik, Paul J.

PY - 2018/9/19

Y1 - 2018/9/19

N2 - Treatment of (iPrPDI)Fe(N2)2 (iPrPDI, 2,6-(2,6-iPr2C6H3Nâ• CMe)2C5H3N) with CO2 and ethylene resulted in the formation of a homologous series of saturated and unsaturated iron carboxylate products, (iPrPDI)Fe(O2CR), the distribution of which depends on the ratio of the reagents. The solid-state and electronic structures of a saturated product, (iPrPDI)Fe(O2CC2H5), were elucidated. Product distributions, deuterium labeling studies, and stoichiometric experiments support initial formation of a five-membered metallalactone intermediate, which undergoes subsequent ethylene insertions to generate macrocyclic metallalactones. Competitive β-hydride elimination, CO2 insertion, or reaction with H2 determines the fate of the metallalactone, the latter accounting for formation of iron complexes with saturated carboxylates. Similar reactivity was observed upon addition of propiolactone and ethylene to (iPrPDI)Fe(N2)2, supporting C-O oxidative addition and C-C bond formation through metallacycle intermediates.

AB - Treatment of (iPrPDI)Fe(N2)2 (iPrPDI, 2,6-(2,6-iPr2C6H3Nâ• CMe)2C5H3N) with CO2 and ethylene resulted in the formation of a homologous series of saturated and unsaturated iron carboxylate products, (iPrPDI)Fe(O2CR), the distribution of which depends on the ratio of the reagents. The solid-state and electronic structures of a saturated product, (iPrPDI)Fe(O2CC2H5), were elucidated. Product distributions, deuterium labeling studies, and stoichiometric experiments support initial formation of a five-membered metallalactone intermediate, which undergoes subsequent ethylene insertions to generate macrocyclic metallalactones. Competitive β-hydride elimination, CO2 insertion, or reaction with H2 determines the fate of the metallalactone, the latter accounting for formation of iron complexes with saturated carboxylates. Similar reactivity was observed upon addition of propiolactone and ethylene to (iPrPDI)Fe(N2)2, supporting C-O oxidative addition and C-C bond formation through metallacycle intermediates.

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AN - SCOPUS:85053710827

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VL - 140

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 37

ER -

Iron-mediated coupling of carbon dioxide and ethylene: Macrocyclic metallalactones enable access to various carboxylates

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