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

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

Research output: Contribution to journalArticlepeer-review

17 Scopus citations

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 Ni0→MIII 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 (Formula presented.))2→M and σ-(Ni−M)1. The latter is an unusual Ni−M σ-bonding molecular orbital that comprises primarily the Ni 4pz and M npz/ns atomic orbitals.

Original languageEnglish (US)
Pages (from-to)7815-7819
Number of pages5
JournalAngewandte Chemie - International Edition
Volume57
Issue number26
DOIs
StatePublished - Jun 25 2018

Bibliographical note

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

Keywords

  • EPR spectroscopy
  • Group 13 elements
  • metalates
  • nickel
  • radicals

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