Heteroleptic Square Planar Cobalt(I/II) Complexes

Yafei Gao, Wei Tsung Lee, Veronica Carta, Chun Hsing Chen, Joshua Telser, Jeremy M. Smith

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

Reduction of the cobalt(II) chloride complex, Ph2B(tBuIm)2Co(THF)Cl (1) in the presence of tBuN≡C affords the diamagnetic, square planar cobalt(I) complex Ph2B(tBuIm)2Co(C≡NtBu)2 (2). This is a rare example of a 16-electron cobalt(I) complex that is structurally related to square planar noble metal complexes. Accordingly, the electronic structure of 2, as calculated by DFT, reveals that the HOMO is largely dz2 in character. Complex 2 is readily oxidized to its cobalt(II) congener [Ph2B(tBuIm)2Co(C=NtBu)2]BPh4 (3-BPh4), whose EPR spectral parameters are characteristic of low-spin d7 with an unpaired electron in an orbital of dz2 parentage. This is also consistent with the results of DFT calculations. Despite its 16-electron configuration and the dz2 parentage of the HOMO, the only tractable reactions of 2 involve one electron oxidation to afford 3.

Original languageEnglish
Article numbere202200675
JournalEuropean Journal of Inorganic Chemistry
Volume26
Issue number8
DOIs
StatePublished - 9 Mar 2023

Keywords

  • Carbene ligands
  • Cobalt
  • Electronic structure
  • Isocyanide ligands
  • Structure elucidation

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