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

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11 p.

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American Chemical Society

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Inorganic Chemistry

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DOI: 10.1021/acs.inorgchem.5b01380, PubMed Central: PMID: 26280846


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 (LN3O2) that provides two closely spaced NNO pincer-type compartments fused together at a central diarylamido unit is described. The trianionic LN3O2 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 (Laux), resulting in complexes with the general form [M2(LN3O2)(Laux)2]+ (where Laux = 1-methyl-benzimidazole (1MeBI), 2,2′-bipyridine (bpy), 4,4′-dibromo-2,2′-bipyridine (bpyBr2), or (S)-2-(4-isopropyl-4,5-dihydrooxazolyl)pyridine (S-iPrOxPy)). The fused nature of the NNO pincer sites results in short metal–metal distances ranging from 2.70 Å for [Co2(LN3O2) (bpy)2]+ to 3.28 Å for [Zn2(LN3O2) (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 Laux ligands, such as S-iPrOxPy, are capable of controlling the helical sense of the LN3O2 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(LN3O2) (bpyBr2)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(LN3O2) (bpy)2]+ results in formation of a S = 1/2 species with a LN3O2-based radical coupled to low-spin Co(II) centers.


Inorganic Chemistry, Vol. 54, No. 47 (2015): 8744-8754. DOI.