Journal
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
Volume 76, Issue 12, Pages 2267-2275Publisher
CHEMICAL SOC JAPAN
DOI: 10.1246/bcsJ.76.2267
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Using p-tert-butylthiacalix[6]arene (H6L) as a clustering ligand, five cluster complexes having Co-5(II) (2), Ni-4(II) (3) and (MNi4II)-Ni-II (M = COII (4), Mn-II (5), and Cu-II (6) cores were synthesized. In all the complexes except for 3, a pinched conic L6- acts as a pentanucleating ligand that involves a similar pyramidally arranged cluster core. Each mixed metal complex 4-6 involves four tetragonally arranged Ni-II ions occupying the basal plane of the pyramid and a M-II ion placed at the apex position. In 3, H2L4- is in a cone conformation and the four Ni-II ions are arranged on the donor surface of H2L4- in a zigzag manner. The mixed metal complexes 4-6 are synthesized by reacting 3 and the appropriate M(AcO)(2) in a 1: 1 ratio with a novel metal-induced core rearrangement occurring. In this reaction, the insertion of a M-II ion at the apex position forces the calixarene to take a cone conformation and the Ni-4(II) array rearranges to form a tetragonal cluster.
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