A new ligand system based on a bipyridine-functionalized calix[4]arene backbone leading to mono- and bimetallic complexes

Reto Dorta, Linda J W Shimon, Haim Rozenberg, Yehoshoa Ben-David, David Milstein

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Abstract

The synthesis of a new ligand system for mono- and bimetallic complexes based on a calixarene is described. Ligand BBPC (3, bis(bipyridine)-calix[4]arene) is obtained in three steps in 40% overall yield by first brominating one of the methyl groups of the 4,4′-dimethyl-2,2′-bipyridine in two steps and subsequently reacting it with p-tertbutylcalix[4]arene under basic conditions. Reaction of BBPC (3) with 2 equiv of [Rh(NBD)2]BF4 or [Rh(NBD)(CH3CN)2]BF4 (NBD = norbornadiene) produces the bimetallic compound BBPC[Rh(NBD)BF4]2 (4). Treatment of the ligand with PdCl2(CH3CN)2 leads to the isolation of the bimetallic complex BBPC[PdCl2]2 (5). When the nickel precursor NiBr2(DME) (DME = dimethoxyethane) is reacted with BBPC, the bimetallic complex BBPC[NiBr2]2 (6) is isolated which, upon crystallization from methanol, gives the mononuclear bis(bipyridine) complex BBPC[NiBr(OMe)] (7). Full characterization includes X-ray structural studies of complexes 4, 5, and 7. The bimetallic compounds 4 and 5 show metal to metal distances of 4.334, Å (for 4) and 3.224, Å (for 5). For all three complexes, unique molecular packing arrangements were found, based on hydrophobic/hydrophilic interactions.

Original languageEnglish
Pages (from-to)3160-3167
Number of pages8
JournalInorganic Chemistry
Volume42
Issue number10
DOIs
Publication statusPublished - May 19 2003

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Ligands
ligands
Calixarenes
Metals
Crystallization
Nickel
metals
Methanol
isolation
methyl alcohol
nickel
crystallization
X rays
synthesis
calix(4)arene
x rays
interactions
palladium chloride
1,2-dimethoxyethane

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

A new ligand system based on a bipyridine-functionalized calix[4]arene backbone leading to mono- and bimetallic complexes. / Dorta, Reto; Shimon, Linda J W; Rozenberg, Haim; Ben-David, Yehoshoa; Milstein, David.

In: Inorganic Chemistry, Vol. 42, No. 10, 19.05.2003, p. 3160-3167.

Research output: Contribution to journalArticle

Dorta, Reto ; Shimon, Linda J W ; Rozenberg, Haim ; Ben-David, Yehoshoa ; Milstein, David. / A new ligand system based on a bipyridine-functionalized calix[4]arene backbone leading to mono- and bimetallic complexes. In: Inorganic Chemistry. 2003 ; Vol. 42, No. 10. pp. 3160-3167.
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abstract = "The synthesis of a new ligand system for mono- and bimetallic complexes based on a calixarene is described. Ligand BBPC (3, bis(bipyridine)-calix[4]arene) is obtained in three steps in 40{\%} overall yield by first brominating one of the methyl groups of the 4,4′-dimethyl-2,2′-bipyridine in two steps and subsequently reacting it with p-tertbutylcalix[4]arene under basic conditions. Reaction of BBPC (3) with 2 equiv of [Rh(NBD)2]BF4 or [Rh(NBD)(CH3CN)2]BF4 (NBD = norbornadiene) produces the bimetallic compound BBPC[Rh(NBD)BF4]2 (4). Treatment of the ligand with PdCl2(CH3CN)2 leads to the isolation of the bimetallic complex BBPC[PdCl2]2 (5). When the nickel precursor NiBr2(DME) (DME = dimethoxyethane) is reacted with BBPC, the bimetallic complex BBPC[NiBr2]2 (6) is isolated which, upon crystallization from methanol, gives the mononuclear bis(bipyridine) complex BBPC[NiBr(OMe)] (7). Full characterization includes X-ray structural studies of complexes 4, 5, and 7. The bimetallic compounds 4 and 5 show metal to metal distances of 4.334, {\AA} (for 4) and 3.224, {\AA} (for 5). For all three complexes, unique molecular packing arrangements were found, based on hydrophobic/hydrophilic interactions.",
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N2 - The synthesis of a new ligand system for mono- and bimetallic complexes based on a calixarene is described. Ligand BBPC (3, bis(bipyridine)-calix[4]arene) is obtained in three steps in 40% overall yield by first brominating one of the methyl groups of the 4,4′-dimethyl-2,2′-bipyridine in two steps and subsequently reacting it with p-tertbutylcalix[4]arene under basic conditions. Reaction of BBPC (3) with 2 equiv of [Rh(NBD)2]BF4 or [Rh(NBD)(CH3CN)2]BF4 (NBD = norbornadiene) produces the bimetallic compound BBPC[Rh(NBD)BF4]2 (4). Treatment of the ligand with PdCl2(CH3CN)2 leads to the isolation of the bimetallic complex BBPC[PdCl2]2 (5). When the nickel precursor NiBr2(DME) (DME = dimethoxyethane) is reacted with BBPC, the bimetallic complex BBPC[NiBr2]2 (6) is isolated which, upon crystallization from methanol, gives the mononuclear bis(bipyridine) complex BBPC[NiBr(OMe)] (7). Full characterization includes X-ray structural studies of complexes 4, 5, and 7. The bimetallic compounds 4 and 5 show metal to metal distances of 4.334, Å (for 4) and 3.224, Å (for 5). For all three complexes, unique molecular packing arrangements were found, based on hydrophobic/hydrophilic interactions.

AB - The synthesis of a new ligand system for mono- and bimetallic complexes based on a calixarene is described. Ligand BBPC (3, bis(bipyridine)-calix[4]arene) is obtained in three steps in 40% overall yield by first brominating one of the methyl groups of the 4,4′-dimethyl-2,2′-bipyridine in two steps and subsequently reacting it with p-tertbutylcalix[4]arene under basic conditions. Reaction of BBPC (3) with 2 equiv of [Rh(NBD)2]BF4 or [Rh(NBD)(CH3CN)2]BF4 (NBD = norbornadiene) produces the bimetallic compound BBPC[Rh(NBD)BF4]2 (4). Treatment of the ligand with PdCl2(CH3CN)2 leads to the isolation of the bimetallic complex BBPC[PdCl2]2 (5). When the nickel precursor NiBr2(DME) (DME = dimethoxyethane) is reacted with BBPC, the bimetallic complex BBPC[NiBr2]2 (6) is isolated which, upon crystallization from methanol, gives the mononuclear bis(bipyridine) complex BBPC[NiBr(OMe)] (7). Full characterization includes X-ray structural studies of complexes 4, 5, and 7. The bimetallic compounds 4 and 5 show metal to metal distances of 4.334, Å (for 4) and 3.224, Å (for 5). For all three complexes, unique molecular packing arrangements were found, based on hydrophobic/hydrophilic interactions.

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