Azadipyrromethene Complexes of d<sup>8</sup> Metal
Centers: Rhodium(I), Iridium(I), Palladium(II), and Platinum(II)
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Abstract
Azadipyrromethenes are blue pigments
that chelate main-group and d-block Lewis acids. Reported here are
azadipyrromethene complexes of d<sup>8</sup> metal centers. The new
compounds are prepared in salt metathesis reactions with chlorinated
organometallic precursors. Sixteen new complexes are reported. The
principal absorption features are an intense peak near 600 nm and
transitions in the ultraviolet; all are characteristic of the azadipyrromethene
chromophore. All compounds are dark solids that yield blue or blue-violet
solutions. Ten complexes are crystallographically characterized. The
structures uniformly show backbone strain, with a <i>meso</i>-nitrogen atom that dilates from pure sp<sup>2</sup>-hybridization.
Structural comparisons are made to related dipyrromethene and tetra-azaporphyrin
complexes. The electron-donating capacity of azadipyrromethene ligands
is evaluated from CO stretching frequencies of three rhodium(I)
carbonyl complexes and from density-functional theory calculations.
Frontier orbitals are confined to the azadipyrromethene ligand. HOMO–LUMO
energy gaps are almost unperturbed from those of the free, anionic
azadipyrromethene