ArticleInorganic chemistry2026
Trans-Influence-Driven Coordination Plasticity in Carbazolide NNN Pincer Nickel(II) Complexes.
Article in Inorganic chemistry, 2026. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.
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Abstract
Carbazolide-based NNN pincer ligands impart a strong electronic trans influence at nickel(II) centers, leading to unusual coordination behavior. A series of Ni(II) complexes supported by CztBu(PyrH)2- reveals pronounced coordination plasticity depending on the ancillary ligand and solvent environment. Halide complexes preferentially form solvated octahedral species in coordinating media and exhibit partial ionization of the Ni-X bond, as supported by salt-metathesis experiments and ionic conductivity measurements. Oxygen-donor ligands promote μ-alkoxide dimer formation with temperature-dependent solution dynamics, while strongly donating ligands such as CF3- and N(SiMe3)2- stabilize classical square-planar geometries. The fluoride complex displays solvent-dependent speciation, with hydrogen-bonding interactions in CHCl3 stabilizing a monomeric square-planar structure. Comparison with diphenylamide analogues confirms that the rigid and strongly donating carbazolide backbone is responsible for this behavior. These results demonstrate how backbone electronics can modulate Ni-ligand lability and coordination geometry in pincer complexes.
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