TY - JOUR
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.
N1 - Publisher Copyright:
© 2018 American Chemical Society.
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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U2 - 10.1021/jacs.8b07558
DO - 10.1021/jacs.8b07558
M3 - Article
C2 - 30173506
AN - SCOPUS:85053710827
SN - 0002-7863
VL - 140
SP - 11589
EP - 11593
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 37
ER -