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The title complex, [Hf(C29H41N2)Cl3], was synthesized from HfCl4 and HC[C(Me)N(iPr2C6H3)]2Li(Et2O) in toluene. The structure is isotypic with those of TiIV and ZrIV complexes reported previously [Nikiforov et al. (2007). Dalton Trans. pp. 4149–4159; Kakaliou et al. (1999). Inorg. Chem. 38, 5964–5977]. There is a crystallographic mirror plane containing the Hf atom, one chloride ligand and the central diketiminate C atom. The HfIV ion has slightly distorted square-pyramidal geometry surrounded by two N atoms from the β-diketiminate ligand and by three Cl anions. Coordination bond lengths are Hf—N = 2.181 (3) Å, and Hf—Cl = 2.3148 (15) and 2.3727 (12) Å.

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In the crystal structure of the title compound, [Pd2(C36H42N6)Cl2](ClO4)2·2C3H7NO·2CH3OH, the dinuclear PdII complex cation lies on an inversion center. Each PdII ion has a distorted square-planar coordination sphere, defined by three N atoms of the macrocyclic ligand and a chloride ion. The PdII complex cations and the methanol mol­ecules are linked through N—H...O and O—H...O hydrogen bonds, forming a zigzag chain along [101]. An intra­molecular N—H...Cl hydrogen bond is also observed.
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