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 language | English |
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Pages (from-to) | 2089-2099 |
Journal | European journal of inorganic chemistry |
Issue number | 11 |
DOIs | |
Publication status | Published - 6 Jun 2005 |
Externally published | Yes |
Keywords
- transition metals
- solid-state structures
- ligand effects
- amidinate
- density functional calculations