Abstract
The structures of metal complexes of two classes of multitopic, “third generation” poly(pyrazolyl)methane ligands, ligands specifically functionalized at the non‐coordinating “back” position, are discussed. For tris(pyrazolyl)methane based [(pz)3C–CH2–O–CH2]nC6H6–n (n = 2, 3, 4 and 6, pz = pyrazolyl ring) ligands, three bonding modes are observed depending on the metal, counterion and solvent: a) the κ3 (tripodal) mode, where all three pyrazolyl rings are coordinated to one metal; b) the κ2‐κ0 mode, with only two pyrazolyl rings bonded to a metallic center while the third is not involved in a donor bond; and c) in a κ2‐κ1 fashion, in which the tris(pyrazolyl)methane unit acts as a bridge between two metals. For bis(pyrazolyl)methane based [CH2–O–CH2–CH(pz)2]nC6H6–n ligands, the main structural arrangement is a mononuclear cationic unit in which two arms of the ligand bond a single silver(I) cation in a tetradentate fashion, giving rise to 16‐ or 17‐member metallacyclic structures.
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