Oxidative Addition of Allylic Halides to Ruthenium(II) Compounds. Preparation, Reactions, and X-ray Crystallographic Structure of Ruthenium(IV)-Allyl Complexes

Hideo Nagashima, Katsunori Mukai, Yusuke Shiota, Keitaro Yamaguchi, Ken Ichi Ara, Takahiko Fukahori, Hiroharu Suzuki, Munetaka Akita, Yoshihiko Moro-Oka, Kenji Itoh

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Abstract

The oxidative addition of allylic halides to (C5R5)RuL2X (R = H, Me; L = CO, PPh3) gave new Ru-(IV)–η3-allyl complexes, (C5R5)RuX23-allyl). An X-ray structure determination was carried out on (C5Me5)RuBr23-C3H5), indicating a pseudo-piano-stool structure having two Br atoms and two terminal carbons of the endo-η3-allyl ligand located at the basal positions. There is a crystal mirror plane bisecting the pentamethylcyclopentadienyl and the π-allyl ligands. Crystal data: orthorhombic, space group P212121, a = 11.738 (1) Å, b = 13.367 (7) Å, c = 9.383 (1) Å, Z = 4, data refined to R = 0.0695. Its1H and13C NMR spectra showed symmetric allyl signals, supporting that the above-described piano-stool structure is maintained even in solution. The oxidative addition of allylic halides to (C5R5)Ru(CO)2X is reversible, since the reductive elimination of allylic halides from the Ru(IV)-allyl complexes proceeded under a CO atmosphere to re-form the Ru(II)–carbonyl compounds. (C5H5)RuCl233C3H5) reacted with DMSO to give the corresponding σ-allyl complex. This result indicates the involvement of σ-π interconversion in the reversible oxidative addition of allylic halides to the Ru(II) precursors. The extrusion of allylic halides from the Ru(IV)-allyl complexes also occurred in hot aromatic hydrocarbons to form cationic Ru(II) complexes, [(C5H5)Ru(arene)]+X-.

Original languageEnglish
Pages (from-to)799-807
Number of pages9
JournalOrganometallics
Volume9
Issue number3
DOIs
Publication statusPublished - Jan 1 1990

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Ruthenium compounds
Ruthenium
Carbon Monoxide
ruthenium
halides
X rays
preparation
Ligands
Aromatic Hydrocarbons
Carbonyl compounds
Crystals
x rays
Dimethyl Sulfoxide
Extrusion
Mirrors
Carbon
ligands
Nuclear magnetic resonance
carbonyl compounds
Atoms

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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Oxidative Addition of Allylic Halides to Ruthenium(II) Compounds. Preparation, Reactions, and X-ray Crystallographic Structure of Ruthenium(IV)-Allyl Complexes. / Nagashima, Hideo; Mukai, Katsunori; Shiota, Yusuke; Yamaguchi, Keitaro; Ara, Ken Ichi; Fukahori, Takahiko; Suzuki, Hiroharu; Akita, Munetaka; Moro-Oka, Yoshihiko; Itoh, Kenji.

In: Organometallics, Vol. 9, No. 3, 01.01.1990, p. 799-807.

Research output: Contribution to journalArticle

Nagashima, Hideo ; Mukai, Katsunori ; Shiota, Yusuke ; Yamaguchi, Keitaro ; Ara, Ken Ichi ; Fukahori, Takahiko ; Suzuki, Hiroharu ; Akita, Munetaka ; Moro-Oka, Yoshihiko ; Itoh, Kenji. / Oxidative Addition of Allylic Halides to Ruthenium(II) Compounds. Preparation, Reactions, and X-ray Crystallographic Structure of Ruthenium(IV)-Allyl Complexes. In: Organometallics. 1990 ; Vol. 9, No. 3. pp. 799-807.
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abstract = "The oxidative addition of allylic halides to (C5R5)RuL2X (R = H, Me; L = CO, PPh3) gave new Ru-(IV)–η3-allyl complexes, (C5R5)RuX2(η3-allyl). An X-ray structure determination was carried out on (C5Me5)RuBr2(η3-C3H5), indicating a pseudo-piano-stool structure having two Br atoms and two terminal carbons of the endo-η3-allyl ligand located at the basal positions. There is a crystal mirror plane bisecting the pentamethylcyclopentadienyl and the π-allyl ligands. Crystal data: orthorhombic, space group P212121, a = 11.738 (1) {\AA}, b = 13.367 (7) {\AA}, c = 9.383 (1) {\AA}, Z = 4, data refined to R = 0.0695. Its1H and13C NMR spectra showed symmetric allyl signals, supporting that the above-described piano-stool structure is maintained even in solution. The oxidative addition of allylic halides to (C5R5)Ru(CO)2X is reversible, since the reductive elimination of allylic halides from the Ru(IV)-allyl complexes proceeded under a CO atmosphere to re-form the Ru(II)–carbonyl compounds. (C5H5)RuCl2(η3-η3C3H5) reacted with DMSO to give the corresponding σ-allyl complex. This result indicates the involvement of σ-π interconversion in the reversible oxidative addition of allylic halides to the Ru(II) precursors. The extrusion of allylic halides from the Ru(IV)-allyl complexes also occurred in hot aromatic hydrocarbons to form cationic Ru(II) complexes, [(C5H5)Ru(arene)]+X-.",
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T1 - Oxidative Addition of Allylic Halides to Ruthenium(II) Compounds. Preparation, Reactions, and X-ray Crystallographic Structure of Ruthenium(IV)-Allyl Complexes

AU - Nagashima, Hideo

AU - Mukai, Katsunori

AU - Shiota, Yusuke

AU - Yamaguchi, Keitaro

AU - Ara, Ken Ichi

AU - Fukahori, Takahiko

AU - Suzuki, Hiroharu

AU - Akita, Munetaka

AU - Moro-Oka, Yoshihiko

AU - Itoh, Kenji

PY - 1990/1/1

Y1 - 1990/1/1

N2 - The oxidative addition of allylic halides to (C5R5)RuL2X (R = H, Me; L = CO, PPh3) gave new Ru-(IV)–η3-allyl complexes, (C5R5)RuX2(η3-allyl). An X-ray structure determination was carried out on (C5Me5)RuBr2(η3-C3H5), indicating a pseudo-piano-stool structure having two Br atoms and two terminal carbons of the endo-η3-allyl ligand located at the basal positions. There is a crystal mirror plane bisecting the pentamethylcyclopentadienyl and the π-allyl ligands. Crystal data: orthorhombic, space group P212121, a = 11.738 (1) Å, b = 13.367 (7) Å, c = 9.383 (1) Å, Z = 4, data refined to R = 0.0695. Its1H and13C NMR spectra showed symmetric allyl signals, supporting that the above-described piano-stool structure is maintained even in solution. The oxidative addition of allylic halides to (C5R5)Ru(CO)2X is reversible, since the reductive elimination of allylic halides from the Ru(IV)-allyl complexes proceeded under a CO atmosphere to re-form the Ru(II)–carbonyl compounds. (C5H5)RuCl2(η3-η3C3H5) reacted with DMSO to give the corresponding σ-allyl complex. This result indicates the involvement of σ-π interconversion in the reversible oxidative addition of allylic halides to the Ru(II) precursors. The extrusion of allylic halides from the Ru(IV)-allyl complexes also occurred in hot aromatic hydrocarbons to form cationic Ru(II) complexes, [(C5H5)Ru(arene)]+X-.

AB - The oxidative addition of allylic halides to (C5R5)RuL2X (R = H, Me; L = CO, PPh3) gave new Ru-(IV)–η3-allyl complexes, (C5R5)RuX2(η3-allyl). An X-ray structure determination was carried out on (C5Me5)RuBr2(η3-C3H5), indicating a pseudo-piano-stool structure having two Br atoms and two terminal carbons of the endo-η3-allyl ligand located at the basal positions. There is a crystal mirror plane bisecting the pentamethylcyclopentadienyl and the π-allyl ligands. Crystal data: orthorhombic, space group P212121, a = 11.738 (1) Å, b = 13.367 (7) Å, c = 9.383 (1) Å, Z = 4, data refined to R = 0.0695. Its1H and13C NMR spectra showed symmetric allyl signals, supporting that the above-described piano-stool structure is maintained even in solution. The oxidative addition of allylic halides to (C5R5)Ru(CO)2X is reversible, since the reductive elimination of allylic halides from the Ru(IV)-allyl complexes proceeded under a CO atmosphere to re-form the Ru(II)–carbonyl compounds. (C5H5)RuCl2(η3-η3C3H5) reacted with DMSO to give the corresponding σ-allyl complex. This result indicates the involvement of σ-π interconversion in the reversible oxidative addition of allylic halides to the Ru(II) precursors. The extrusion of allylic halides from the Ru(IV)-allyl complexes also occurred in hot aromatic hydrocarbons to form cationic Ru(II) complexes, [(C5H5)Ru(arene)]+X-.

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