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Title: Quantification of Ni–N–O Bond Angles and NO Activation by X-ray Emission Spectroscopy

Abstract

Here, a series of β-diketiminate Ni–NO complexes with a range of NO binding modes and oxidation states were studied by X-ray emission spectroscopy (XES). The results demonstrate that XES can directly probe and distinguish end-on vs side-on NO coordination modes as well as one-electron NO reduction. Density functional theory (DFT) calculations show that the transition from the NO 2s2s σ* orbital has higher intensity for end-on NO coordination than for side-on NO coordination, whereas the 2s2s σ orbital has lower intensity. XES calculations in which the Ni–N–O bond angle was fixed over the range from 80° to 176° suggest that differences in NO coordination angles of ~10° could be experimentally distinguished. Calculations of Cu nitrite reductase (NiR) demonstrate the utility of XES for characterizing NO intermediates in metalloenzymes. This work shows the capability of XES to distinguish NO coordination modes and oxidation states at Ni and highlights applications in quantifying small molecule activation in enzymes.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2];  [3];  [3]; ORCiD logo [4]; ORCiD logo [1]
+ Show Author Affiliations
  1. California State Polytechnic University, Pomona, CA (United States)
  2. Georgetown Univ., Washington, DC (United States); Indian Institute of Science Education and Research Thiruvananthapuram, Kerala (India)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  4. Georgetown Univ., Washington, DC (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); National Institutes of Health (NIH)
OSTI Identifier:
1798890
Grant/Contract Number:  
AC02-76SF00515; 1847926; CHE160059; R01GM126205; P41GM103393
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 60; Journal Issue: 2; 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

Citation Formats

Phu, Phan N., Gutierrez, Carlos E., Kundu, Subrata, Sokaras, Dimosthenis, Kroll, Thomas, Warren, Timothy H., and Stieber, S. Chantal E. Quantification of Ni–N–O Bond Angles and NO Activation by X-ray Emission Spectroscopy. United States: N. p., 2020. Web. doi:10.1021/acs.inorgchem.0c02724.
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Phu, Phan N., Gutierrez, Carlos E., Kundu, Subrata, Sokaras, Dimosthenis, Kroll, Thomas, Warren, Timothy H., & Stieber, S. Chantal E. Quantification of Ni–N–O Bond Angles and NO Activation by X-ray Emission Spectroscopy. United States. https://doi.org/10.1021/acs.inorgchem.0c02724
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Phu, Phan N., Gutierrez, Carlos E., Kundu, Subrata, Sokaras, Dimosthenis, Kroll, Thomas, Warren, Timothy H., and Stieber, S. Chantal E. Tue . "Quantification of Ni–N–O Bond Angles and NO Activation by X-ray Emission Spectroscopy". United States. https://doi.org/10.1021/acs.inorgchem.0c02724. https://www.osti.gov/servlets/purl/1798890.
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@article{osti_1798890,
title = {Quantification of Ni–N–O Bond Angles and NO Activation by X-ray Emission Spectroscopy},
author = {Phu, Phan N. and Gutierrez, Carlos E. and Kundu, Subrata and Sokaras, Dimosthenis and Kroll, Thomas and Warren, Timothy H. and Stieber, S. Chantal E.},
abstractNote = {Here, a series of β-diketiminate Ni–NO complexes with a range of NO binding modes and oxidation states were studied by X-ray emission spectroscopy (XES). The results demonstrate that XES can directly probe and distinguish end-on vs side-on NO coordination modes as well as one-electron NO reduction. Density functional theory (DFT) calculations show that the transition from the NO 2s2s σ* orbital has higher intensity for end-on NO coordination than for side-on NO coordination, whereas the 2s2s σ orbital has lower intensity. XES calculations in which the Ni–N–O bond angle was fixed over the range from 80° to 176° suggest that differences in NO coordination angles of ~10° could be experimentally distinguished. Calculations of Cu nitrite reductase (NiR) demonstrate the utility of XES for characterizing NO intermediates in metalloenzymes. This work shows the capability of XES to distinguish NO coordination modes and oxidation states at Ni and highlights applications in quantifying small molecule activation in enzymes.},
doi = {10.1021/acs.inorgchem.0c02724},
journal = {Inorganic Chemistry},
number = 2,
volume = 60,
place = {United States},
year = {Tue Dec 29 00:00:00 EST 2020},
month = {Tue Dec 29 00:00:00 EST 2020}
}
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https://doi.org/10.1021/acs.inorgchem.0c02724
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