p-tert-Butylthiacalix[6]arene as a Clustering Ligand. Syntheses and Structures of CoII5, NiII4, and Mixed-Metal MIINiII4 (M = Mn, Co, and Cu) Cluster Complexes, and a Novel Metal-Induced Cluster Core Rearrangement

Using p-tert-butylthiacalix[6]arene (H6L) as a clustering ligand, five cluster complexes having CoII5 (2), NiII4 (3) and MIINiII4 (M = CoII (4), MnII (5), and CuII (6)) cores were synthesized. In all the complexes except for 3, a pinched conic L6− acts as a pentanucleating ligand that involves a sim...

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Published inBulletin of the Chemical Society of Japan Vol. 76; no. 12; pp. 2267 - 2275
Main Authors Kajiwara, Takashi, Shinagawa, Reiko, Ito, Tasuku, Kon, Noriyoshi, Iki, Nobuhiko, Miyano, Sotaro
Format Journal Article
LanguageEnglish
Published Tokyo The Chemical Society of Japan 2003
Chemical Society of Japan
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Abstract Using p-tert-butylthiacalix[6]arene (H6L) as a clustering ligand, five cluster complexes having CoII5 (2), NiII4 (3) and MIINiII4 (M = CoII (4), MnII (5), and CuII (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 NiII ions occupying the basal plane of the pyramid and a MII ion placed at the apex position. In 3, H2L4− is in a cone conformation and the four NiII 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 MII ion at the apex position forces the calixarene to take a cone conformation and the NiII4 array rearranges to form a tetragonal cluster.
AbstractList Abstract Using p-tert-butylthiacalix[6]arene (H6L) as a clustering ligand, five cluster complexes having CoII5 (2), NiII4 (3) and MIINiII4 (M = CoII (4), MnII (5), and CuII (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 NiII ions occupying the basal plane of the pyramid and a MII ion placed at the apex position. In 3, H2L4− is in a cone conformation and the four NiII 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 MII ion at the apex position forces the calixarene to take a cone conformation and the NiII4 array rearranges to form a tetragonal cluster.
Using p-tert-butylthiacalix[6]arene (H6L) as a clustering ligand, five cluster complexes having CoII5 (2), NiII4 (3) and MIINiII4 (M = CoII (4), MnII (5), and CuII (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 NiII ions occupying the basal plane of the pyramid and a MII ion placed at the apex position. In 3, H2L4- is in a cone conformation and the four NiII 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 MII ion at the apex position forces the calixarene to take a cone conformation and the NiII4 array rearranges to form a tetragonal cluster.
Using p-tert-butylthiacalix[6]arene (H6L) as a clustering ligand, five cluster complexes having CoII5 (2), NiII4 (3) and MIINiII4 (M = CoII (4), MnII (5), and CuII (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 NiII ions occupying the basal plane of the pyramid and a MII ion placed at the apex position. In 3, H2L4− is in a cone conformation and the four NiII 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 MII ion at the apex position forces the calixarene to take a cone conformation and the NiII4 array rearranges to form a tetragonal cluster.
Author Shinagawa, Reiko
Kon, Noriyoshi
Ito, Tasuku
Miyano, Sotaro
Kajiwara, Takashi
Iki, Nobuhiko
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  organization: 2 Department of Biomolecular Engineering, Graduate School of Engineering, Tohoku UniversityAramaki, Aoba-ku, Sendai 980-8579
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Snippet Using p-tert-butylthiacalix[6]arene (H6L) as a clustering ligand, five cluster complexes having CoII5 (2), NiII4 (3) and MIINiII4 (M = CoII (4), MnII (5), and...
Abstract Using p-tert-butylthiacalix[6]arene (H6L) as a clustering ligand, five cluster complexes having CoII5 (2), NiII4 (3) and MIINiII4 (M = CoII (4), MnII...
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Title p-tert-Butylthiacalix[6]arene as a Clustering Ligand. Syntheses and Structures of CoII5, NiII4, and Mixed-Metal MIINiII4 (M = Mn, Co, and Cu) Cluster Complexes, and a Novel Metal-Induced Cluster Core Rearrangement
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