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Title: Spectroscopic and Computational Investigation of Low-Spin MnIII Bis(scorpionate) Complexes

Abstract

Six-coordinate Mn III complexes are typically high-spin (S = 2), however, the scorpionate ligand, both in its traditional, hydridotris(pyrazolyl)borate form, Tp - and Tp* - (the latter with 3,5dimethylpyrazole substituents) and in an aryltris(carbene)borate (i.e. , N -heterocyclic carbene, NHC) form, [Ph(MeIm) 3B] -, (MeIm = 3-methylimidazole) lead to formation of bis(scorpionate) complexes of Mn III with spin triplet ground states; three of which were investigated herein: [Tp 2Mn]SbF 6 (1SBF 6), [Tp* 2Mn]SbF 6 (2SBF 6), and [{Ph(MeIm) 3B} 2Mn]CF 3SO 3 (3CF 3SO 3). These trigonally symmetric complexes were studied experimentally by magnetic circular dichroism (MCD) spectroscopy (the propensity of 3 to oxidize to Mn IV precluded collection of useful MCD data) including variable temperatures and fields (VTVH-MCD) and computationally by ab initio CASSCF/NEVPT2 methods. These combined experimental and theoretical techniques establish the 3A 2g electronic ground state for the three complexes, and provide information on the energy of the “conventional” high-spin excited state ( 5E g) and other, triplet excited states. These results show the electronic effect of pyrazole ring substituents in comparing 1 and 2. The tunability of the scorpionate ligand, even by perhaps the simplest change (from pyrazole in 1 to 3,5-dimethylpyrazole in 2) ismore » quantitatively manifested through perturbations in ligand-field excited-state energies that impact ground-state zero-field splittings. The comparison with the NHC donor is much more dramatic. In 3, the stronger σ-donor properties of the NHC lead to a quantitatively different electronic structure, so that the lowest lying spin triplet excited state, 3E g, is much closer in energy to the ground state than in 1 or 2. The zero-field splitting (zfs) parameters of the three complexes were calculated and in the case of 1 and 2 compare closely to experiment (lower by < 10%, < 2 cm -1 in absolute terms); for 3 the large magnitude zfs is reproduced, although there is ambiguity about its sign. The comprehensive picture obtained for these bis(scorpionate) Mn III complexes thus provides quantitative insight into the role played by the scorpionate ligand in stabilizing unusual electronic structures.« less

Authors:
 [1];  [2];  [3];  [1]; ORCiD logo [4]
  1. Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemistry
  2. New Mexico State Univ., Las Cruces, NM (United States). Dept. of Chemistry and Biochemistry
  3. New Mexico State Univ., Las Cruces, NM (United States). Dept. of Chemistry and Biochemistry; Indiana Univ., Bloomington, IN (United States). Dept. of Chemistry
  4. Roosevelt Univ., Chicago, IL (United States). Dept. of Biological, Chemical and Physical Sciences
Publication Date:
Research Org.:
New Mexico State Univ., Las Cruces, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); National Institutes of Health (NIH)
Contributing Org.:
Univ. of California, Berkeley, CA (United States)
OSTI Identifier:
1467007
Grant/Contract Number:  
FG02-08ER15996; CHE‐1056470; T32 GM08545
Resource Type:
Accepted Manuscript
Journal Name:
European Journal of Inorganic Chemistry
Additional Journal Information:
Journal Volume: 2016; Journal Issue: 15-16; Journal ID: ISSN 1434-1948
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; scorpionate ligands; magnetic circular dichroism; electronic structure; zero-field splitting; ab initio calculations

Citation Formats

Colmer, Hannah E., Margarit, Charles G., Smith, Jeremy M., Jackson, Timothy A., and Telser, Joshua. Spectroscopic and Computational Investigation of Low-Spin MnIII Bis(scorpionate) Complexes. United States: N. p., 2015. Web. doi:10.1002/ejic.201501250.
Colmer, Hannah E., Margarit, Charles G., Smith, Jeremy M., Jackson, Timothy A., & Telser, Joshua. Spectroscopic and Computational Investigation of Low-Spin MnIII Bis(scorpionate) Complexes. United States. doi:10.1002/ejic.201501250.
Colmer, Hannah E., Margarit, Charles G., Smith, Jeremy M., Jackson, Timothy A., and Telser, Joshua. Wed . "Spectroscopic and Computational Investigation of Low-Spin MnIII Bis(scorpionate) Complexes". United States. doi:10.1002/ejic.201501250. https://www.osti.gov/servlets/purl/1467007.
@article{osti_1467007,
title = {Spectroscopic and Computational Investigation of Low-Spin MnIII Bis(scorpionate) Complexes},
author = {Colmer, Hannah E. and Margarit, Charles G. and Smith, Jeremy M. and Jackson, Timothy A. and Telser, Joshua},
abstractNote = {Six-coordinate MnIII complexes are typically high-spin (S = 2), however, the scorpionate ligand, both in its traditional, hydridotris(pyrazolyl)borate form, Tp- and Tp*- (the latter with 3,5dimethylpyrazole substituents) and in an aryltris(carbene)borate (i.e. , N -heterocyclic carbene, NHC) form, [Ph(MeIm)3B]-, (MeIm = 3-methylimidazole) lead to formation of bis(scorpionate) complexes of MnIII with spin triplet ground states; three of which were investigated herein: [Tp2Mn]SbF6 (1SBF6), [Tp*2Mn]SbF6 (2SBF6), and [{Ph(MeIm)3B}2Mn]CF3SO3 (3CF3SO3). These trigonally symmetric complexes were studied experimentally by magnetic circular dichroism (MCD) spectroscopy (the propensity of 3 to oxidize to MnIV precluded collection of useful MCD data) including variable temperatures and fields (VTVH-MCD) and computationally by ab initio CASSCF/NEVPT2 methods. These combined experimental and theoretical techniques establish the 3A2g electronic ground state for the three complexes, and provide information on the energy of the “conventional” high-spin excited state (5Eg) and other, triplet excited states. These results show the electronic effect of pyrazole ring substituents in comparing 1 and 2. The tunability of the scorpionate ligand, even by perhaps the simplest change (from pyrazole in 1 to 3,5-dimethylpyrazole in 2) is quantitatively manifested through perturbations in ligand-field excited-state energies that impact ground-state zero-field splittings. The comparison with the NHC donor is much more dramatic. In 3, the stronger σ-donor properties of the NHC lead to a quantitatively different electronic structure, so that the lowest lying spin triplet excited state, 3Eg, is much closer in energy to the ground state than in 1 or 2. The zero-field splitting (zfs) parameters of the three complexes were calculated and in the case of 1 and 2 compare closely to experiment (lower by < 10%, < 2 cm-1 in absolute terms); for 3 the large magnitude zfs is reproduced, although there is ambiguity about its sign. The comprehensive picture obtained for these bis(scorpionate) MnIII complexes thus provides quantitative insight into the role played by the scorpionate ligand in stabilizing unusual electronic structures.},
doi = {10.1002/ejic.201501250},
journal = {European Journal of Inorganic Chemistry},
number = 15-16,
volume = 2016,
place = {United States},
year = {2015},
month = {12}
}

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