Nickel, palladium, and platinum complexes of η 5- cyclopentadienide C 60R 5 ligands. Kinetic and thermodynamic stabilization effects of the C 60Ph 5 ligand

Yoichiro Kuninobu, Yutaka Matsuo, Motoki Toganoh, Masaya Sawamura, Eiichi Nakamura

Research output: Contribution to journalArticle

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Abstract

The nickel-, palladium-, and platinum-RFC p complexes η 5-RFC p)(η 3-allylic) (3b, RFC p = C 60R 5, R = Me, allylic = methallyl; 4a, R = Ph, allylic = allyl; 4b, R = Ph, allylic = methallyl), Pd(η 5- RFC p)(η 3-allylic) (7a, R = Me, allylic = allyl; 7b, R = Me, allylic = methallyl; 7c, R = Me, allylic = crotyl; 8a, R = Ph, allylic = allyl; 8b, R = Ph, allylic = methallyl; 8c, R = Ph, allylic = crotyl), and Pt(η 5-RFC p)(η 3-methallyl) (9, R = Me; 10, R = Ph), were synthesized by transmetalation between K(RFC p) (R = Me, Ph) and [Ni(allylic)Br] 2, [Pd(allylic)Cl] 2, or [Pt(methallyl)Cl] 2 in THF at 25 °C for 10 min. The nickel-PhFC p complexes 4a,b are unusually more stable toward molecular oxygen than the corresponding simple nickel cyclopentadienides and survive in air for many hours at elevated temperature. The crystal structures and the electrochemical properties of the palladium complexes suggest that the unusual stability of the PhFC p complexes is due to the kinetic stabilization effect of the five Ph groups surrounding the metal atom and the thermodynamic stabilization effect of the electron-withdrawing fullerene moiety, hence suggesting new opportunities for the synthesis of otherwise unstable organometallic compounds.

Original languageEnglish
Pages (from-to)3259-3266
Number of pages8
JournalOrganometallics
Volume23
Issue number13
DOIs
Publication statusPublished - Jun 21 2004

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Palladium
Platinum
Nickel
palladium
platinum
Stabilization
stabilization
nickel
Thermodynamics
Ligands
thermodynamics
ligands
Kinetics
kinetics
Organometallic Compounds
Fullerenes
Molecular oxygen
Electrochemical properties
Crystal structure
Metals

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Nickel, palladium, and platinum complexes of η 5- cyclopentadienide C 60R 5 ligands. Kinetic and thermodynamic stabilization effects of the C 60Ph 5 ligand. / Kuninobu, Yoichiro; Matsuo, Yutaka; Toganoh, Motoki; Sawamura, Masaya; Nakamura, Eiichi.

In: Organometallics, Vol. 23, No. 13, 21.06.2004, p. 3259-3266.

Research output: Contribution to journalArticle

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abstract = "The nickel-, palladium-, and platinum-RFC p complexes η 5-RFC p)(η 3-allylic) (3b, RFC p = C 60R 5, R = Me, allylic = methallyl; 4a, R = Ph, allylic = allyl; 4b, R = Ph, allylic = methallyl), Pd(η 5- RFC p)(η 3-allylic) (7a, R = Me, allylic = allyl; 7b, R = Me, allylic = methallyl; 7c, R = Me, allylic = crotyl; 8a, R = Ph, allylic = allyl; 8b, R = Ph, allylic = methallyl; 8c, R = Ph, allylic = crotyl), and Pt(η 5-RFC p)(η 3-methallyl) (9, R = Me; 10, R = Ph), were synthesized by transmetalation between K(RFC p) (R = Me, Ph) and [Ni(allylic)Br] 2, [Pd(allylic)Cl] 2, or [Pt(methallyl)Cl] 2 in THF at 25 °C for 10 min. The nickel-PhFC p complexes 4a,b are unusually more stable toward molecular oxygen than the corresponding simple nickel cyclopentadienides and survive in air for many hours at elevated temperature. The crystal structures and the electrochemical properties of the palladium complexes suggest that the unusual stability of the PhFC p complexes is due to the kinetic stabilization effect of the five Ph groups surrounding the metal atom and the thermodynamic stabilization effect of the electron-withdrawing fullerene moiety, hence suggesting new opportunities for the synthesis of otherwise unstable organometallic compounds.",
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T1 - Nickel, palladium, and platinum complexes of η 5- cyclopentadienide C 60R 5 ligands. Kinetic and thermodynamic stabilization effects of the C 60Ph 5 ligand

AU - Kuninobu, Yoichiro

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AU - Toganoh, Motoki

AU - Sawamura, Masaya

AU - Nakamura, Eiichi

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N2 - The nickel-, palladium-, and platinum-RFC p complexes η 5-RFC p)(η 3-allylic) (3b, RFC p = C 60R 5, R = Me, allylic = methallyl; 4a, R = Ph, allylic = allyl; 4b, R = Ph, allylic = methallyl), Pd(η 5- RFC p)(η 3-allylic) (7a, R = Me, allylic = allyl; 7b, R = Me, allylic = methallyl; 7c, R = Me, allylic = crotyl; 8a, R = Ph, allylic = allyl; 8b, R = Ph, allylic = methallyl; 8c, R = Ph, allylic = crotyl), and Pt(η 5-RFC p)(η 3-methallyl) (9, R = Me; 10, R = Ph), were synthesized by transmetalation between K(RFC p) (R = Me, Ph) and [Ni(allylic)Br] 2, [Pd(allylic)Cl] 2, or [Pt(methallyl)Cl] 2 in THF at 25 °C for 10 min. The nickel-PhFC p complexes 4a,b are unusually more stable toward molecular oxygen than the corresponding simple nickel cyclopentadienides and survive in air for many hours at elevated temperature. The crystal structures and the electrochemical properties of the palladium complexes suggest that the unusual stability of the PhFC p complexes is due to the kinetic stabilization effect of the five Ph groups surrounding the metal atom and the thermodynamic stabilization effect of the electron-withdrawing fullerene moiety, hence suggesting new opportunities for the synthesis of otherwise unstable organometallic compounds.

AB - The nickel-, palladium-, and platinum-RFC p complexes η 5-RFC p)(η 3-allylic) (3b, RFC p = C 60R 5, R = Me, allylic = methallyl; 4a, R = Ph, allylic = allyl; 4b, R = Ph, allylic = methallyl), Pd(η 5- RFC p)(η 3-allylic) (7a, R = Me, allylic = allyl; 7b, R = Me, allylic = methallyl; 7c, R = Me, allylic = crotyl; 8a, R = Ph, allylic = allyl; 8b, R = Ph, allylic = methallyl; 8c, R = Ph, allylic = crotyl), and Pt(η 5-RFC p)(η 3-methallyl) (9, R = Me; 10, R = Ph), were synthesized by transmetalation between K(RFC p) (R = Me, Ph) and [Ni(allylic)Br] 2, [Pd(allylic)Cl] 2, or [Pt(methallyl)Cl] 2 in THF at 25 °C for 10 min. The nickel-PhFC p complexes 4a,b are unusually more stable toward molecular oxygen than the corresponding simple nickel cyclopentadienides and survive in air for many hours at elevated temperature. The crystal structures and the electrochemical properties of the palladium complexes suggest that the unusual stability of the PhFC p complexes is due to the kinetic stabilization effect of the five Ph groups surrounding the metal atom and the thermodynamic stabilization effect of the electron-withdrawing fullerene moiety, hence suggesting new opportunities for the synthesis of otherwise unstable organometallic compounds.

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