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Electronic Structure Investigation o...

Lutz, Sean A.

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Electronic Structure Investigation of Low Valent Novel Iron Complexes: Mechanisms of C-H Activation and Magnetic Studies.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Electronic Structure Investigation of Low Valent Novel Iron Complexes: Mechanisms of C-H Activation and Magnetic Studies./
Author:	Lutz, Sean A.
Published:	Ann Arbor : ProQuest Dissertations & Theses, : 2020,
Description:	113 p.
Notes:	Source: Dissertations Abstracts International, Volume: 82-03, Section: B.
Contained By:	Dissertations Abstracts International82-03B.
Subject:	Inorganic chemistry. -
Online resource:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=28086719
ISBN:	9798664735062

Electronic Structure Investigation of Low Valent Novel Iron Complexes: Mechanisms of C-H Activation and Magnetic Studies.
Lutz, Sean A.

Electronic Structure Investigation of Low Valent Novel Iron Complexes: Mechanisms of C-H Activation and Magnetic Studies. - Ann Arbor : ProQuest Dissertations & Theses, 2020 - 113 p.

Source: Dissertations Abstracts International, Volume: 82-03, Section: B.

Thesis (Ph.D.)--Indiana University, 2020.

This item must not be sold to any third party vendors.

The density functional theory (DFT) investigation of C-H activation by low valent bis(carbene)borate iron complexes was undergone to determine the role of spin states in the mechanism. The high spin ground state for the unsaturated four-coordinate [Ph2B(tBuIm)2FeX2]- (where X = CO, neopentyl, or N2) complexes undergo C-H activation only through spin crossover to the low spin surface. The classical two-electron chemistry steps (i.e. oxidative addition and reductive elimination) were found to only be possible on the low spin surface.When the ancillary ligands are carbonyls, the high spin formally iron(0) [Ph2B(tBuIm)2Fe(CO)2]- (1) complex activated the sp3 C-H bonds of the tert-butyl substituents of the N-heterocyclic carbene ligands to form a low-spin six-coordinate iron(II) hydride complex. Surprisingly, this reaction was found to be equilibrium. DFT results indicate that spin crossover occurs before the transition state resulting in the mechanism being consistent with two-state reactivity.Replacing the ancillary ligand with neopentyl and dinitrogen, the high spin [Ph2B(tBuIm)2FeCH2tBu(N2)]- (2) was catalytically active for the isomerization of 1-hexene to 2-hexene even in the presence of strong σ bases. The unique electronic structure of 2 reveals frontier molecular orbitals that are optimized for π-accepting ligands over strong σ bases. The mechanism for alkene isomerization by 2 was found to be consistent with the allyl mechanism. However, both oxidative addition and reductive elimination steps were found to only be possible on the low spin surface.

ISBN: 9798664735062Subjects--Topical Terms:

3173556
Inorganic chemistry.
Subjects--Index Terms:

Electronic Structure

Electronic Structure Investigation of Low Valent Novel Iron Complexes: Mechanisms of C-H Activation and Magnetic Studies.
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245 1 0 $a Electronic Structure Investigation of Low Valent Novel Iron Complexes: Mechanisms of C-H Activation and Magnetic Studies.
260 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 2020
300 $a 113 p.
500 $a Source: Dissertations Abstracts International, Volume: 82-03, Section: B.
500 $a Advisor: Smith, Jeremy.
502 $a Thesis (Ph.D.)--Indiana University, 2020.
506 $a This item must not be sold to any third party vendors.
520 $a The density functional theory (DFT) investigation of C-H activation by low valent bis(carbene)borate iron complexes was undergone to determine the role of spin states in the mechanism. The high spin ground state for the unsaturated four-coordinate [Ph2B(tBuIm)2FeX2]- (where X = CO, neopentyl, or N2) complexes undergo C-H activation only through spin crossover to the low spin surface. The classical two-electron chemistry steps (i.e. oxidative addition and reductive elimination) were found to only be possible on the low spin surface.When the ancillary ligands are carbonyls, the high spin formally iron(0) [Ph2B(tBuIm)2Fe(CO)2]- (1) complex activated the sp3 C-H bonds of the tert-butyl substituents of the N-heterocyclic carbene ligands to form a low-spin six-coordinate iron(II) hydride complex. Surprisingly, this reaction was found to be equilibrium. DFT results indicate that spin crossover occurs before the transition state resulting in the mechanism being consistent with two-state reactivity.Replacing the ancillary ligand with neopentyl and dinitrogen, the high spin [Ph2B(tBuIm)2FeCH2tBu(N2)]- (2) was catalytically active for the isomerization of 1-hexene to 2-hexene even in the presence of strong σ bases. The unique electronic structure of 2 reveals frontier molecular orbitals that are optimized for π-accepting ligands over strong σ bases. The mechanism for alkene isomerization by 2 was found to be consistent with the allyl mechanism. However, both oxidative addition and reductive elimination steps were found to only be possible on the low spin surface.
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