Synthesis and Characterization of (DIPPCCC)Fe Complexes: A Zwitterionic Metalation Method and CO2 Reactivity

Bailey J. Jackson; Daniel C. Najera; Ellen M. Matson; Toby J. Woods; Jeffery A. Bertke; Alison R. Fout

doi:10.1021/acs.organomet.9b00271

Synthesis and Characterization of (^DIPPCCC)Fe Complexes: A Zwitterionic Metalation Method and CO₂ Reactivity

Bailey J. Jackson, Daniel C. Najera, Ellen M. Matson, Toby J. Woods, Jeffery A. Bertke, Alison R. Fout

Chemistry

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

Abstract

The synthesis and characterization of a series of novel iron complexes has been accomplished using a monoanionic pincer bis(carbene) ligand framework. Metalation first proceeded through an isolated Fe(II) zwitterionic intermediate that was subsequently reduced in situ to Fe(0) to facilitate oxidative addition of the aryl C-H bond, generating the Fe^II-H complexes. Varying the L-type ligand on these complexes exhibited profound effects, as observed by IR and ¹H NMR spectroscopy. Higher oxidation states of Fe could also be supported in this ligand framework, as evidenced by the isolation of two Fe(III) complexes. Treating an Fe^II-H complex with CO₂ generated an Fe-formate complex (κ²-OOCH) from insertion into the Fe^II-H bond. The independent synthesis of this molecule was accomplished by treating Fe^II-Cl with excess NaOOCH.

Original language	English (US)
Pages (from-to)	2943-2952
Number of pages	10
Journal	Organometallics
Volume	38
Issue number	15
DOIs	https://doi.org/10.1021/acs.organomet.9b00271
State	Published - Aug 12 2019

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/acs.organomet.9b00271

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title = "Synthesis and Characterization of (DIPPCCC)Fe Complexes: A Zwitterionic Metalation Method and CO2 Reactivity",

abstract = "The synthesis and characterization of a series of novel iron complexes has been accomplished using a monoanionic pincer bis(carbene) ligand framework. Metalation first proceeded through an isolated Fe(II) zwitterionic intermediate that was subsequently reduced in situ to Fe(0) to facilitate oxidative addition of the aryl C-H bond, generating the FeII-H complexes. Varying the L-type ligand on these complexes exhibited profound effects, as observed by IR and 1H NMR spectroscopy. Higher oxidation states of Fe could also be supported in this ligand framework, as evidenced by the isolation of two Fe(III) complexes. Treating an FeII-H complex with CO2 generated an Fe-formate complex (κ2-OOCH) from insertion into the FeII-H bond. The independent synthesis of this molecule was accomplished by treating FeII-Cl with excess NaOOCH.",

author = "Jackson, {Bailey J.} and Najera, {Daniel C.} and Matson, {Ellen M.} and Woods, {Toby J.} and Bertke, {Jeffery A.} and Fout, {Alison R.}",

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T2 - A Zwitterionic Metalation Method and CO2 Reactivity

AU - Jackson, Bailey J.

AU - Najera, Daniel C.

AU - Matson, Ellen M.

AU - Woods, Toby J.

AU - Bertke, Jeffery A.

AU - Fout, Alison R.

PY - 2019/8/12

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N2 - The synthesis and characterization of a series of novel iron complexes has been accomplished using a monoanionic pincer bis(carbene) ligand framework. Metalation first proceeded through an isolated Fe(II) zwitterionic intermediate that was subsequently reduced in situ to Fe(0) to facilitate oxidative addition of the aryl C-H bond, generating the FeII-H complexes. Varying the L-type ligand on these complexes exhibited profound effects, as observed by IR and 1H NMR spectroscopy. Higher oxidation states of Fe could also be supported in this ligand framework, as evidenced by the isolation of two Fe(III) complexes. Treating an FeII-H complex with CO2 generated an Fe-formate complex (κ2-OOCH) from insertion into the FeII-H bond. The independent synthesis of this molecule was accomplished by treating FeII-Cl with excess NaOOCH.

AB - The synthesis and characterization of a series of novel iron complexes has been accomplished using a monoanionic pincer bis(carbene) ligand framework. Metalation first proceeded through an isolated Fe(II) zwitterionic intermediate that was subsequently reduced in situ to Fe(0) to facilitate oxidative addition of the aryl C-H bond, generating the FeII-H complexes. Varying the L-type ligand on these complexes exhibited profound effects, as observed by IR and 1H NMR spectroscopy. Higher oxidation states of Fe could also be supported in this ligand framework, as evidenced by the isolation of two Fe(III) complexes. Treating an FeII-H complex with CO2 generated an Fe-formate complex (κ2-OOCH) from insertion into the FeII-H bond. The independent synthesis of this molecule was accomplished by treating FeII-Cl with excess NaOOCH.

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