Neutral Formazan Ligands Bound to the fac-(CO)₃Re(I) Fragment: Structural, Spectroscopic, and Computational Studies

Metal complexes with ligands that coordinate via the nitrogen atom of azo (N═N) or imino (C═N) groups are of interest due to their π-acceptor properties and redox-active nature, which leads to interesting (opto)electronic properties and reactivity. Here, we describe the synthesis and characterization of rhenium(I) tricarbonyl complexes with neutral N,N-bidentate formazans, which possess both N═N and C═N fragments within the ligand backbone (Ar¹-NH-N═C(R³)-N═N-Ar⁵). The compounds were synthesized by reacting equimolar amounts of [ReBr(CO)₅] and the corresponding neutral formazan. X-ray crystallographic and spectroscopic (IR, NMR) characterization confirmed the generation of formazan-type species with the structure fac-[ReBr(CO)₃(κ²-N²,N⁴(Ar¹-N¹H-N²═C(R³)-N³═N⁴-Ar⁵))]. The formazan ligand coordinates the metal center in the 'open' form, generating a five-membered chelate ring with a pendant NH arm. The electronic absorption and emission properties of these complexes are governed by the presence of low-lying π*-orbitals on the ligand as shown by DFT calculations. The high orbital mixing between the metal and ligand results in photophysical properties that contrast to those observed in fac-[ReBr(CO)₃(L,L)] species with α-diimine ligands.