Thyminato-bridged cyclic tetranuclear rhodium(III) complexes containing a sodium, calcium or lanthanoid ion as a template metal core

Mika Sakate, Ayana Kashima, Haruka Hosoda, Yukinari Sunatsuki, Hiromi Ota, Akira Fuyuhiro, Takayoshi Suzuki

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Abstract

Reactions of [(Cp*Rh)2(μ-OH)3]OH (Cp*5-C5Me5 -) and thymine (=H2thym) in methanol in the presence or absence of a certain metal salt were examined. From the reaction mixture without any template metal salt, a dinuclear hydroxido-bridged complex bearing monodentate monodeprotonated thyminato ligands, [(Cp*Rh(Hthym-κN 1))2(μ-OH)2], was isolated after recrystallization from water. In the presence of a metal salt MX n (=NaPF6, NaBF4, NaNO3, Ca(NO3)2, Ca(ClO4)2, La(NO3)3, Eu(NO3)3, Dy(NO3)3 and Er(NO3)3) were deposited orange crystals (1P, 1B, 1N, 2N, 2C, 3N, 4N, 5N and 6N, respectively) which consist of a thyminato(2-)-bridged tetranuclear Cp*Rh complex incorporating a M n + cation, [(Cp*Rh)4(μ-thym)4M] n +. All complexes were characterized by the single-crystal X-ray diffraction method, which revealed that homochiral aggregations of four RhIII centers were achieved to give metallacalix[4]arene-type clusters. It was also observed that the bridging modes of thym2- ligands were dependent on the template metal ion. In the Na+-incorporated clusters (1X, X = P, B or N) a thym2- ligand bridged two RhIII and the third Na+ ions with a μ3-1κN 1:2κ2 N 3,O 2:3κO 2 mode, while in the Ln3+ analogs (Ln=La, Eu, Dy or Er: 3N-6N) thym2- exhibited a different bridging mode, μ3-1κN 1:2κ2 N 3,O 4:3κO 2. In the cases of Ca2+-incorporated clusters, the bridging mode is further dependent on the associated anion; only the μ3-1κN 1:2κ2 N 3,O 2:3κO 2-type cluster was obtained in the NO3 - salt (2N), but the ClO4 - salt (2C) afforded both types of the bridging clusters piled up alternatively in the crystals. The tetranuclear structures with a template metal cation, [(Cp*Rh)4(μ-thym)4M] n +, are maintained in solution. The magnetic behaviors of the Dy3+- and Er3+-incorporated complexes (5N and 6N) are also reported.

Original languageEnglish
JournalInorganica Chimica Acta
DOIs
Publication statusAccepted/In press - Nov 30 2015

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Lanthanoid Series Elements
Rhodium
rhodium
calcium
Calcium
templates
Salts
Metals
Sodium
sodium
Ions
salts
metals
Ligands
ions
ligands
Cations
Bearings (structural)
Positive ions
cations

Keywords

  • Bridging isomers
  • Crystal structure
  • Heterometallic complexes
  • Metallacalix[n]arene
  • Template synthesis

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

@article{2bef8e4f93ee4d7189a6faaf72e277aa,
title = "Thyminato-bridged cyclic tetranuclear rhodium(III) complexes containing a sodium, calcium or lanthanoid ion as a template metal core",
abstract = "Reactions of [(Cp*Rh)2(μ-OH)3]OH (Cp* =η5-C5Me5 -) and thymine (=H2thym) in methanol in the presence or absence of a certain metal salt were examined. From the reaction mixture without any template metal salt, a dinuclear hydroxido-bridged complex bearing monodentate monodeprotonated thyminato ligands, [(Cp*Rh(Hthym-κN 1))2(μ-OH)2], was isolated after recrystallization from water. In the presence of a metal salt MX n (=NaPF6, NaBF4, NaNO3, Ca(NO3)2, Ca(ClO4)2, La(NO3)3, Eu(NO3)3, Dy(NO3)3 and Er(NO3)3) were deposited orange crystals (1P, 1B, 1N, 2N, 2C, 3N, 4N, 5N and 6N, respectively) which consist of a thyminato(2-)-bridged tetranuclear Cp*Rh complex incorporating a M n + cation, [(Cp*Rh)4(μ-thym)4M] n +. All complexes were characterized by the single-crystal X-ray diffraction method, which revealed that homochiral aggregations of four RhIII centers were achieved to give metallacalix[4]arene-type clusters. It was also observed that the bridging modes of thym2- ligands were dependent on the template metal ion. In the Na+-incorporated clusters (1X, X = P, B or N) a thym2- ligand bridged two RhIII and the third Na+ ions with a μ3-1κN 1:2κ2 N 3,O 2:3κO 2 mode, while in the Ln3+ analogs (Ln=La, Eu, Dy or Er: 3N-6N) thym2- exhibited a different bridging mode, μ3-1κN 1:2κ2 N 3,O 4:3κO 2. In the cases of Ca2+-incorporated clusters, the bridging mode is further dependent on the associated anion; only the μ3-1κN 1:2κ2 N 3,O 2:3κO 2-type cluster was obtained in the NO3 - salt (2N), but the ClO4 - salt (2C) afforded both types of the bridging clusters piled up alternatively in the crystals. The tetranuclear structures with a template metal cation, [(Cp*Rh)4(μ-thym)4M] n +, are maintained in solution. The magnetic behaviors of the Dy3+- and Er3+-incorporated complexes (5N and 6N) are also reported.",
keywords = "Bridging isomers, Crystal structure, Heterometallic complexes, Metallacalix[n]arene, Template synthesis",
author = "Mika Sakate and Ayana Kashima and Haruka Hosoda and Yukinari Sunatsuki and Hiromi Ota and Akira Fuyuhiro and Takayoshi Suzuki",
year = "2015",
month = "11",
day = "30",
doi = "10.1016/j.ica.2016.01.023",
language = "English",
journal = "Inorganica Chimica Acta",
issn = "0020-1693",
publisher = "Elsevier BV",

}

TY - JOUR

T1 - Thyminato-bridged cyclic tetranuclear rhodium(III) complexes containing a sodium, calcium or lanthanoid ion as a template metal core

AU - Sakate, Mika

AU - Kashima, Ayana

AU - Hosoda, Haruka

AU - Sunatsuki, Yukinari

AU - Ota, Hiromi

AU - Fuyuhiro, Akira

AU - Suzuki, Takayoshi

PY - 2015/11/30

Y1 - 2015/11/30

N2 - Reactions of [(Cp*Rh)2(μ-OH)3]OH (Cp* =η5-C5Me5 -) and thymine (=H2thym) in methanol in the presence or absence of a certain metal salt were examined. From the reaction mixture without any template metal salt, a dinuclear hydroxido-bridged complex bearing monodentate monodeprotonated thyminato ligands, [(Cp*Rh(Hthym-κN 1))2(μ-OH)2], was isolated after recrystallization from water. In the presence of a metal salt MX n (=NaPF6, NaBF4, NaNO3, Ca(NO3)2, Ca(ClO4)2, La(NO3)3, Eu(NO3)3, Dy(NO3)3 and Er(NO3)3) were deposited orange crystals (1P, 1B, 1N, 2N, 2C, 3N, 4N, 5N and 6N, respectively) which consist of a thyminato(2-)-bridged tetranuclear Cp*Rh complex incorporating a M n + cation, [(Cp*Rh)4(μ-thym)4M] n +. All complexes were characterized by the single-crystal X-ray diffraction method, which revealed that homochiral aggregations of four RhIII centers were achieved to give metallacalix[4]arene-type clusters. It was also observed that the bridging modes of thym2- ligands were dependent on the template metal ion. In the Na+-incorporated clusters (1X, X = P, B or N) a thym2- ligand bridged two RhIII and the third Na+ ions with a μ3-1κN 1:2κ2 N 3,O 2:3κO 2 mode, while in the Ln3+ analogs (Ln=La, Eu, Dy or Er: 3N-6N) thym2- exhibited a different bridging mode, μ3-1κN 1:2κ2 N 3,O 4:3κO 2. In the cases of Ca2+-incorporated clusters, the bridging mode is further dependent on the associated anion; only the μ3-1κN 1:2κ2 N 3,O 2:3κO 2-type cluster was obtained in the NO3 - salt (2N), but the ClO4 - salt (2C) afforded both types of the bridging clusters piled up alternatively in the crystals. The tetranuclear structures with a template metal cation, [(Cp*Rh)4(μ-thym)4M] n +, are maintained in solution. The magnetic behaviors of the Dy3+- and Er3+-incorporated complexes (5N and 6N) are also reported.

AB - Reactions of [(Cp*Rh)2(μ-OH)3]OH (Cp* =η5-C5Me5 -) and thymine (=H2thym) in methanol in the presence or absence of a certain metal salt were examined. From the reaction mixture without any template metal salt, a dinuclear hydroxido-bridged complex bearing monodentate monodeprotonated thyminato ligands, [(Cp*Rh(Hthym-κN 1))2(μ-OH)2], was isolated after recrystallization from water. In the presence of a metal salt MX n (=NaPF6, NaBF4, NaNO3, Ca(NO3)2, Ca(ClO4)2, La(NO3)3, Eu(NO3)3, Dy(NO3)3 and Er(NO3)3) were deposited orange crystals (1P, 1B, 1N, 2N, 2C, 3N, 4N, 5N and 6N, respectively) which consist of a thyminato(2-)-bridged tetranuclear Cp*Rh complex incorporating a M n + cation, [(Cp*Rh)4(μ-thym)4M] n +. All complexes were characterized by the single-crystal X-ray diffraction method, which revealed that homochiral aggregations of four RhIII centers were achieved to give metallacalix[4]arene-type clusters. It was also observed that the bridging modes of thym2- ligands were dependent on the template metal ion. In the Na+-incorporated clusters (1X, X = P, B or N) a thym2- ligand bridged two RhIII and the third Na+ ions with a μ3-1κN 1:2κ2 N 3,O 2:3κO 2 mode, while in the Ln3+ analogs (Ln=La, Eu, Dy or Er: 3N-6N) thym2- exhibited a different bridging mode, μ3-1κN 1:2κ2 N 3,O 4:3κO 2. In the cases of Ca2+-incorporated clusters, the bridging mode is further dependent on the associated anion; only the μ3-1κN 1:2κ2 N 3,O 2:3κO 2-type cluster was obtained in the NO3 - salt (2N), but the ClO4 - salt (2C) afforded both types of the bridging clusters piled up alternatively in the crystals. The tetranuclear structures with a template metal cation, [(Cp*Rh)4(μ-thym)4M] n +, are maintained in solution. The magnetic behaviors of the Dy3+- and Er3+-incorporated complexes (5N and 6N) are also reported.

KW - Bridging isomers

KW - Crystal structure

KW - Heterometallic complexes

KW - Metallacalix[n]arene

KW - Template synthesis

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U2 - 10.1016/j.ica.2016.01.023

DO - 10.1016/j.ica.2016.01.023

M3 - Article

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

ER -