Bimetallic Complexes Supported by a Redox-Active Ligand with Fused Pincer-Type Coordination Sites

The remarkable chemistry of mononuclear complexes featuring tridentate, meridionally chelating "pincer" ligands has stimulated the development of ligand frameworks containing multiple pincer sites. Here, the coordination chemistry of a novel pentadentate ligand (L(N3O2)) that provides two closely spaced NNO pincer-type compartments fused together at a central diarylamido unit is described. The trianionic L(N3O2) chelate supports homobimetallic structures in which each M(II) ion (M = Co, Cu, Zn) is bound in a meridional fashion by the bridging diarylamido N atom and O,N-donors of the salicyaldimine arms. The metal centers are also coordinated by a mono- or bidentate auxiliary ligand (L(aux)), resulting in complexes with the general form [M2(L(N3O2))(L(aux))2](+) (where L(aux) = 1-methyl-benzimidazole (1MeBI), 2,2'-bipyridine (bpy), 4,4'-dibromo-2,2'-bipyridine (bpy(Br2)), or (S)-2-(4-isopropyl-4,5-dihydrooxazolyl)pyridine (S-(iPr)OxPy)). The fused nature of the NNO pincer sites results in short metal-metal distances ranging from 2.70 Å for [Co2(L(N3O2)) (bpy)2](+) to 3.28 Å for [Zn2(L(N3O2)) (bpy)2](+), as revealed by X-ray crystallography. The complexes possess C2 symmetry due to the twisting of the aryl rings of the μ-NAr2 core; spectroscopic studies indicate that chiral L(aux) ligands, such as S-(iPr)OxPy, are capable of controlling the helical sense of the L(N3O2) scaffold. Since the four- or five-coordinate M(II) centers are linked solely by the amido moiety, each features an open coordination site in the intermetallic region, allowing for the possibility of metal-metal cooperativity in small-molecule activation. Indeed, the dicobalt(II) complex [Co2(L(N3O2)) (bpy(Br2))2](+) reacts with O2 to yield a dicobalt(III) species with a μ-1,2-peroxo ligand. The bpy-containing complexes exhibit rich electrochemical properties due to multiple metal- and ligand-based redox events across a wide (3.0 V) potential window. Using electron paramagnetic resonance (EPR) spectroscopy and density functional theory (DFT), it was determined that one-electron oxidation of [Co2(L(N3O2)) (bpy)2](+) results in formation of a S = 1/2 species with a L(N3O2)-based radical coupled to low-spin Co(II) centers.