Formal Nickelate(−I) Complexes Supported by Group 13 Ions
Abstract
Abstract Formal nickelate(−I) complexes bearing Group 13 metalloligands (M=Al and Ga) were isolated. These 17 e − complexes were synthesized by one‐electron reduction of the corresponding Ni 0 →M III precursors, and were investigated by single‐crystal X‐ray diffraction, EPR spectroscopy, and quantum chemical calculations. Collectively, the experimental and computational data support: 1) the strengthening of the Ni−M bond upon one‐electron reduction, and 2) the delocalization of the unpaired spin across the Ni and M atoms. An intriguing electronic configuration is revealed where three valence electrons occupy two σ‐type bonding interactions: Ni(3d ) 2 →M and σ‐(Ni−M) 1 . The latter is an unusual Ni−M σ‐bonding molecular orbital that comprises primarily the Ni 4p z and M np z /ns atomic orbitals.
- Authors:
-
[1];
[1];
[2];
[1];
[1]
- Department of Chemistry and Supercomputing Institute University of Minnesota 207 Pleasant St. SE Minneapolis MN 55455 USA
- Max-Planck-Institut für chemische Energiekonversion Stiftstraße 34–36 45470 Mülheim an der Ruhr Germany
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1439264
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Angewandte Chemie
- Additional Journal Information:
- Journal Name: Angewandte Chemie Journal Volume: 130 Journal Issue: 26; Journal ID: ISSN 0044-8249
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Vollmer, Matthew V., Xie, Jing, Cammarota, Ryan C., Young, Jr., Victor G., Bill, Eckhard, Gagliardi, Laura, and Lu, Connie C. Formal Nickelate(−I) Complexes Supported by Group 13 Ions. Germany: N. p., 2018.
Web. doi:10.1002/ange.201803356.
Vollmer, Matthew V., Xie, Jing, Cammarota, Ryan C., Young, Jr., Victor G., Bill, Eckhard, Gagliardi, Laura, & Lu, Connie C. Formal Nickelate(−I) Complexes Supported by Group 13 Ions. Germany. https://doi.org/10.1002/ange.201803356
Vollmer, Matthew V., Xie, Jing, Cammarota, Ryan C., Young, Jr., Victor G., Bill, Eckhard, Gagliardi, Laura, and Lu, Connie C. Mon .
"Formal Nickelate(−I) Complexes Supported by Group 13 Ions". Germany. https://doi.org/10.1002/ange.201803356.
@article{osti_1439264,
title = {Formal Nickelate(−I) Complexes Supported by Group 13 Ions},
author = {Vollmer, Matthew V. and Xie, Jing and Cammarota, Ryan C. and Young, Jr., Victor G. and Bill, Eckhard and Gagliardi, Laura and Lu, Connie C.},
abstractNote = {Abstract Formal nickelate(−I) complexes bearing Group 13 metalloligands (M=Al and Ga) were isolated. These 17 e − complexes were synthesized by one‐electron reduction of the corresponding Ni 0 →M III precursors, and were investigated by single‐crystal X‐ray diffraction, EPR spectroscopy, and quantum chemical calculations. Collectively, the experimental and computational data support: 1) the strengthening of the Ni−M bond upon one‐electron reduction, and 2) the delocalization of the unpaired spin across the Ni and M atoms. An intriguing electronic configuration is revealed where three valence electrons occupy two σ‐type bonding interactions: Ni(3d ) 2 →M and σ‐(Ni−M) 1 . The latter is an unusual Ni−M σ‐bonding molecular orbital that comprises primarily the Ni 4p z and M np z /ns atomic orbitals.},
doi = {10.1002/ange.201803356},
journal = {Angewandte Chemie},
number = 26,
volume = 130,
place = {Germany},
year = {Mon May 28 00:00:00 EDT 2018},
month = {Mon May 28 00:00:00 EDT 2018}
}
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