Scrutinizing formally NiIVcenters through the lenses of core spectroscopy, molecular orbital theory, and valence bond theory

Author:

DiMucci Ida M.1,Titus Charles J.2,Nordlund Dennis3,Bour James R.4,Chong Eugene4,Grigas Dylan P.1,Hu Chi-Herng5,Kosobokov Mikhail D.6,Martin Caleb D.7ORCID,Mirica Liviu M.5ORCID,Nebra Noel8,Vicic David A.6ORCID,Yorks Lydia L.6ORCID,Yruegas Sam7ORCID,MacMillan Samantha N.1ORCID,Shearer Jason9ORCID,Lancaster Kyle M.1ORCID

Affiliation:

1. Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, 162 Sciences Drive, Ithaca, NY 14853, USA

2. Department of Physics, Stanford University, Stanford, California 94305, USA

3. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA

4. Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, USA

5. Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA

6. Department of Chemistry, Lehigh University, Bethlehem, Pennsylvania 18015, USA

7. Department of Chemistry and Biochemistry, Baylor University, Waco, Texas 76798, USA

8. Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA), Université Paul Sabatier, CNRS, 118 Route de Narbonne, 31062 Toulouse, France

9. Department of Chemistry, Trinity University, San Antonio, Texas 78212-7200, USA

Abstract

Nickel K- and L2,3-edge X-ray absorption spectra (XAS) are discussed for coordinated nickel centers spanning formal oxidation states from II to IV. The ensuing analysis indicates that a physical “+4” oxidation state is untenable for coordinated Ni.

Funder

Welch Foundation

Agence Nationale de la Recherche

National Science Foundation

National Institutes of Health

Publisher

Royal Society of Chemistry (RSC)

Subject

General Chemistry

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