The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure

Binuclear rhodium(III) and iridium(III) monoselenocarboxylates: Synthesis, spectroscopy and structure of an ortho-metallated iridium complex featuring an IrCCC(μ-Se) chelate ring

“…Summarizing, the ortho-metallation observed here follows a general tendency of iridium(III) to engage in cyclometallation and of [Cp*Ir] 2+ in particular to stabilize highly basic and p donating chelate configurations [28][29][30][31][32] such as 1,2-enediamido. To our knowledge, however, it is the first time that an [IrCCCSe] fivemembered chelate ring has been obtained, distinguished by three sp 2 carbon centres (including one aromatic carbanion C and one uncoordinated carbonyl function), and by one bridging selenolato-Se.…”

Hybrid α‐Diimine/Bis(chalcogenoether) Ligands for Copper(I) and Copper(II) Complexes

“…Metal compounds of α‐diimines frequently undergo reversible reduction to radical complexes, however, Hartl and co‐workers have shown that dimerization can follow in some cases . A similar reactivity is assumed here because monomeric radical complexes could not be detected by EPR on reduction.…”

“…Compound 1 thus acts only as a bidentate chelate ligand towards Cu I due to the weakness of Cu I –O bonds, especially with uncharged central oxygen atoms. While such compounds have been shown to exhibit metal‐to‐ligand charge transfer in low‐lying excited states, the bond parameters of 4 + suggest only little π back donation as indicated by slightly lengthened C=N (1.30 Å) and shortened central C–C bonds (1.484 Å), confirmed experimentally and computationally (Table ). The dihedral angle between the two N–Cu–N chelate sections is 67.44°, right between the values found for related [Cu( t BuN=C–C=N t Bu) 2 ](Br) at 89.5°) and [Cu(MesN=C–C=NMes) 2 ](BF 4 ) at 51.1°.…”

α‐Dialdimine Complexes of Rhodium(I) and Iridium(I): Their Reactivity with Dioxygen and Dihydrogen

“…The corresponding bond lengths found for 2 and 3 seem to be closer to the nonreduced form of the bpa‐2H ligand. However, deduction of the electronic properties of diimine ligands from their bond distances is not always unambiguous 3c…”