Formal Nickelate(−I) Complexes Supported by Group 13 Ions

Vollmer, Matthew V.; Xie, Jing; Cammarota, Ryan C.; Young, Jr., Victor G.; Bill, Eckhard; Gagliardi, Laura; Lu, Connie C.

doi:10.1002/ange.201803356

Title: Formal Nickelate(−I) Complexes Supported by Group 13 Ions

Journal Article · Mon May 28 00:00:00 EDT 2018 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201803356· OSTI ID:1439264

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^[1]; Cammarota, Ryan C. ^[1]; Young, Jr., Victor G. ^[1];

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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

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.

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Sponsoring Organization:: USDOE

OSTI ID:: 1439264

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 130 Journal Issue: 26; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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