skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

This content will become publicly available on July 8, 2020

Title: A Dimeric Hydride-Bridged Complex with Geometrically Distinct Iron Centers Giving Rise to an S = 3 Ground State

Abstract

Structural and spectroscopic characterization of the dimeric iron hydride complex [Ph 2B( tBuIm) 2FeH] 2 reveals an unusual structure in which a tetrahedral iron(II) site (S = 2) is connected to a square planar iron(II) site (S = 1) by two bridging hydride ligands. Magnetic susceptibility reveals strong ferromagnetic coupling between iron centers, with a coupling constant of J = +110(12) cm -1, to give an S = 3 ground state. High-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy confirms this model. A qualitative molecular orbital analysis of the electronic structure, as supported by electronic structure calculations, reveals that the observed spin configuration results from the orthogonal alignment of two geometrically distinct four-coordinate iron fragments held together by highly covalent hydride ligands.

Authors:
 [1]; ORCiD logo [2];  [1];  [1];  [1];  [3]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [4]; ORCiD logo [1]
  1. Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405, United States
  2. National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida 32310, United States
  3. Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States
  4. Department of Biological, Physical and Health Sciences, Roosevelt University, Chicago, Illinois 60605, United States
Publication Date:
Research Org.:
Indiana Univ., Bloomington, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1594027
Grant/Contract Number:  
[SC0019466]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
[ Journal Volume: 141; Journal Issue: 30]; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hickey, Anne K., Greer, Samuel M., Valdez-Moreira, Juan A., Lutz, Sean A., Pink, Maren, DeGayner, Jordan A., Harris, T. David, Hill, Stephen, Telser, Joshua, and Smith, Jeremy M. A Dimeric Hydride-Bridged Complex with Geometrically Distinct Iron Centers Giving Rise to an S = 3 Ground State. United States: N. p., 2019. Web. doi:10.1021/jacs.9b04389.
Hickey, Anne K., Greer, Samuel M., Valdez-Moreira, Juan A., Lutz, Sean A., Pink, Maren, DeGayner, Jordan A., Harris, T. David, Hill, Stephen, Telser, Joshua, & Smith, Jeremy M. A Dimeric Hydride-Bridged Complex with Geometrically Distinct Iron Centers Giving Rise to an S = 3 Ground State. United States. doi:10.1021/jacs.9b04389.
Hickey, Anne K., Greer, Samuel M., Valdez-Moreira, Juan A., Lutz, Sean A., Pink, Maren, DeGayner, Jordan A., Harris, T. David, Hill, Stephen, Telser, Joshua, and Smith, Jeremy M. Mon . "A Dimeric Hydride-Bridged Complex with Geometrically Distinct Iron Centers Giving Rise to an S = 3 Ground State". United States. doi:10.1021/jacs.9b04389.
@article{osti_1594027,
title = {A Dimeric Hydride-Bridged Complex with Geometrically Distinct Iron Centers Giving Rise to an S = 3 Ground State},
author = {Hickey, Anne K. and Greer, Samuel M. and Valdez-Moreira, Juan A. and Lutz, Sean A. and Pink, Maren and DeGayner, Jordan A. and Harris, T. David and Hill, Stephen and Telser, Joshua and Smith, Jeremy M.},
abstractNote = {Structural and spectroscopic characterization of the dimeric iron hydride complex [Ph2B(tBuIm)2FeH]2 reveals an unusual structure in which a tetrahedral iron(II) site (S = 2) is connected to a square planar iron(II) site (S = 1) by two bridging hydride ligands. Magnetic susceptibility reveals strong ferromagnetic coupling between iron centers, with a coupling constant of J = +110(12) cm-1, to give an S = 3 ground state. High-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy confirms this model. A qualitative molecular orbital analysis of the electronic structure, as supported by electronic structure calculations, reveals that the observed spin configuration results from the orthogonal alignment of two geometrically distinct four-coordinate iron fragments held together by highly covalent hydride ligands.},
doi = {10.1021/jacs.9b04389},
journal = {Journal of the American Chemical Society},
number = [30],
volume = [141],
place = {United States},
year = {2019},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on July 8, 2020
Publisher's Version of Record

Save / Share: