First-row transition metal bis(amidinate) complexes; Planar four-coordination of Fe-II enforced by sterically demanding aryl substituents

CA Nijhuis, E Jellema, TJJ Sciarone, A Meetsma, PHM Budzelaar, B Hessen*

*Corresponding author for this work

Research output: Contribution to journalReview articleAcademicpeer-review

61 Citations (Scopus)

Abstract

The sterically hindered benzamidinate ligand [PhC(NAr)2] – (Ar = 2,6-iPr2C6H3) has been employed to prepare bis(amidinate) complexes [{PhC(NAr)2}2M] of the divalent first-row transition metals Cr–Ni (1–5). For Cr (planar), Mn and Co (tetrahedral) the observed structures follow the electronic preference for the metal ion in its highest spin multiplicity, as determined by DFT calculations. Remarkably, the Fe derivative adopts a distorted planar structure while retaining the high-spin (S = 2) configuration. This rare combination is due to reduced interligand steric interactions in the planar vs. the tetrahedral structure, combined with a relatively small electronic preference of FeII for the tetrahedral environment. Thus, the simple bidentate ligand N,N-diarylbenzamidinate provides a convenient means to make this unusual species accessible for further study.
Original languageEnglish
Pages (from-to)2089-2099
JournalEuropean journal of inorganic chemistry
Issue number11
DOIs
Publication statusPublished - 6 Jun 2005
Externally publishedYes

Keywords

  • transition metals
  • solid-state structures
  • ligand effects
  • amidinate
  • density functional calculations

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