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Title: Experimental and Theoretical Comparison of Transition-Metal and Actinide Tetravalent Schiff Base Coordination Complexes

Abstract

A series of homoleptic tetravalent transition-metal and actinide Schiff-base coordination complexes, ML2 {M = Zr, Hf, Th, U; L = N,N'-bis[(4,4'-diethylamino)salicylidene]-1,2-phenylenediamine}, have been synthesized that feature a rigid phenyl backbone. These complexes create the opportunity for comparing a series of complexes containing metal cations in the formal IV+ oxidation state by structural, spectroscopic, and theoretical analysis that also incorporate the previously reported Ce(IV) and Pu(IV) analogues. X-ray crystallographic analysis reveals that all complexes are isomorphous and feature a co-facial ligand geometry. TD-DFT and other quantum mechanical methods were used to explore bonding differences across between the complexes, and resulting calculated absorbance spectra for ML2 are in good agreement with the experimental data. The computational results also suggest that U(IV) and Pu(IV) analogs have more covalent character in their bonding than found with the other metal cations reported here.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [1]
  1. Florida State Univ., Tallahassee, FL (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Actinide Science & Technology (CAST); Florida State Univ., Tallahassee, FL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1566500
Grant/Contract Number:  
SC0016568
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 24; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nuclear; defects; mechanical behavior; corrosion; charge transport; superconductivity; magnetism and spin physics; separations; geophysics/geochemistry; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (predictive); synthesis (scalable processing)

Citation Formats

Klamm, Bonnie E., Windorff, Cory J., Celis-Barros, Cristian, Marsh, Matthew L., Meeker, David S., and Albrecht-Schmitt, Thomas E. Experimental and Theoretical Comparison of Transition-Metal and Actinide Tetravalent Schiff Base Coordination Complexes. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.8b02700.
Klamm, Bonnie E., Windorff, Cory J., Celis-Barros, Cristian, Marsh, Matthew L., Meeker, David S., & Albrecht-Schmitt, Thomas E. Experimental and Theoretical Comparison of Transition-Metal and Actinide Tetravalent Schiff Base Coordination Complexes. United States. https://doi.org/10.1021/acs.inorgchem.8b02700
Klamm, Bonnie E., Windorff, Cory J., Celis-Barros, Cristian, Marsh, Matthew L., Meeker, David S., and Albrecht-Schmitt, Thomas E. Fri . "Experimental and Theoretical Comparison of Transition-Metal and Actinide Tetravalent Schiff Base Coordination Complexes". United States. https://doi.org/10.1021/acs.inorgchem.8b02700. https://www.osti.gov/servlets/purl/1566500.
@article{osti_1566500,
title = {Experimental and Theoretical Comparison of Transition-Metal and Actinide Tetravalent Schiff Base Coordination Complexes},
author = {Klamm, Bonnie E. and Windorff, Cory J. and Celis-Barros, Cristian and Marsh, Matthew L. and Meeker, David S. and Albrecht-Schmitt, Thomas E.},
abstractNote = {A series of homoleptic tetravalent transition-metal and actinide Schiff-base coordination complexes, ML2 {M = Zr, Hf, Th, U; L = N,N'-bis[(4,4'-diethylamino)salicylidene]-1,2-phenylenediamine}, have been synthesized that feature a rigid phenyl backbone. These complexes create the opportunity for comparing a series of complexes containing metal cations in the formal IV+ oxidation state by structural, spectroscopic, and theoretical analysis that also incorporate the previously reported Ce(IV) and Pu(IV) analogues. X-ray crystallographic analysis reveals that all complexes are isomorphous and feature a co-facial ligand geometry. TD-DFT and other quantum mechanical methods were used to explore bonding differences across between the complexes, and resulting calculated absorbance spectra for ML2 are in good agreement with the experimental data. The computational results also suggest that U(IV) and Pu(IV) analogs have more covalent character in their bonding than found with the other metal cations reported here.},
doi = {10.1021/acs.inorgchem.8b02700},
journal = {Inorganic Chemistry},
number = 24,
volume = 57,
place = {United States},
year = {2018},
month = {11}
}

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