Title: Electronic structure studies reveal 4f/5d mixing and its effect on bonding characteristics in Ce-imido and -oxo complexes

Abstract

This study presents the role of 5d orbitals in the bonding, and electronic and magnetic structure of Ce imido and oxo complexes synthesized with a tris(hydroxylaminato) [((2-^{BuNO)C₆H₄CH₂)₃N]3- (TriNO_x3-) ligand framework, including the reported synthesis and characterization of two new alkali metal-capped Ce oxo species. X-ray spectroscopy measurements reveal that the imido and oxo materials exhibit an intermediate valent ground state of the Ce, displaying hallmark features in the Ce L_III absorption of partial f-orbital occupancy that are relatively constant for all measured compounds. These spectra feature a double peak consistent with other formal Ce(iv) compounds. Magnetic susceptibility measurements reveal enhanced levels of temperature-independent paramagnetism (TIP). In contrast to systems with direct bonding to an aromatic ligand, no clear correlation between the level of TIP and f-orbital occupancy is observed. CASSCF calculations defy a conventional van Vleck explanation of the TIP, indicating a single-reference ground state with no low-lying triplet excited state, despite accurately predicting the measured values of f-orbital occupancy. The calculations do, however, predict strong 4f/5d hybridization. In fact, within these complexes, despite having similar f-orbital occupancies and therefore levels of 4f/5d hybridization, the d-state distributions vary depending on the bonding motif (Ce═O vs. Ce═N) of the complex, andmore » can also be fine-tuned based on varying alkali metal cation capping species. This system therefore provides a platform for understanding the characteristic nature of Ce multiple bonds and potential impact that the associated d-state distribution may have on resulting reactivity.}« less

Authors:

Moreau, Liane M.  ^[1];

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• Search DOE PAGES for ORCID "0000-0003-4381-8753"

Lapsheva, Ekaterina ^[2]; Amaro-Estrada, Jorge I.  ^[3];

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Gau, Michael R.  ^[2];

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Carroll, Patrick J. ^[2]; Manor, Brian C. ^[2]; Qiao, Yusen  ^[4];

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Yang, Qiaomu  ^[2];

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Lukens, Wayne W.  ^[1];

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Sokaras, Dimosthenis ^[5]; Schelter, Eric J.  ^[2];

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Maron, Laurent  ^[3];

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Booth, Corwin H.  ^[1]

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• Search DOE PAGES for ORCID "0000-0001-6827-0080"

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+ Show Author Affiliations

1. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
2. Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104, USA
3. LPCNO, UMR 5215, CNRS, INSA, UPS, Université de Toulouse, 31000 Toulouse, France
4. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA, Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104, USA
5. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA

Publication Date:

Wed Feb 09 00:00:00 EST 2022

Research Org.:

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Org.:

USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

OSTI Identifier:

1841784

Alternate Identifier(s):

OSTI ID: 1855367; OSTI ID: 1862013

Grant/Contract Number:  

AC02-05CH11231; AC02-76SF00515; SC0020169

Resource Type:

Published Article

Journal Name:

Chemical Science

Additional Journal Information:

Journal Name: Chemical Science Journal Volume: 13 Journal Issue: 6; Journal ID: ISSN 2041-6520

Publisher:

Royal Society of Chemistry (RSC)

Country of Publication:

United Kingdom

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY