Synthesis of [AsPh4][Fe3(CO)9(μ-CO)(μ3-HBCl)] by Oxidative Chloride Substitution of [Fe3(CO)93-HBCO)]2-

Louise E. Crascall, B. H.S. Thimmappa, Arnold L. Rheingold, Robert Ostrander, Thomas P. Fehlner

Research output: Contribution to journalArticle

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Abstract

The deprotonation of (μ-H)Fe3(CO)9(μ-CO)(μ3-HBH) with n-butyllithium yields the dianionic complex [Li]2[Fe3(CO)93-HBCO)], which has been spectroscopically characterized. In contrast to the facile reprotonation of closely related ferraboranes, protonation of [Li]2[Fe3(CO)93-HBCO)] leads to decomposition. On the other hand, reaction of this dianionic complex with 2 equiv of FeCl3 gives a good yield of [Li][Fe3(CO)9(μ-CO)(μ3-HBCl). Metathesis with [AsPh4][Cl] yields [AsPh4][Fe3(CO)9(μ-CO)(μ3-HBCl)], which has been crystallographically characterized (triclinic, P1, a = 9.534(3) Å, b = 13.305(4) Å, c = 15.225(4) Å, α = 104.39(2)°, β = 103.56(2)°, γ = 99.23(2)°, V = 1768.7(8) Å3, Z = 2). Comparison with the analogous osmium clusters, as well as isoelectronic organometallic clusters, reveals relationships among their structures, properties, and energetics.

Original languageEnglish
Pages (from-to)2153-2158
Number of pages6
JournalOrganometallics
Volume13
Issue number6
DOIs
Publication statusPublished - 01-06-1994

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Carbon Monoxide
Chlorides
Substitution reactions
chlorides
substitutes
osmium
metathesis
synthesis
decomposition
Osmium
Deprotonation
Protonation
Organometallics
Decomposition

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Crascall, Louise E. ; Thimmappa, B. H.S. ; Rheingold, Arnold L. ; Ostrander, Robert ; Fehlner, Thomas P. / Synthesis of [AsPh4][Fe3(CO)9(μ-CO)(μ3-HBCl)] by Oxidative Chloride Substitution of [Fe3(CO)93-HBCO)]2-. In: Organometallics. 1994 ; Vol. 13, No. 6. pp. 2153-2158.
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abstract = "The deprotonation of (μ-H)Fe3(CO)9(μ-CO)(μ3-HBH) with n-butyllithium yields the dianionic complex [Li]2[Fe3(CO)9(μ3-HBCO)], which has been spectroscopically characterized. In contrast to the facile reprotonation of closely related ferraboranes, protonation of [Li]2[Fe3(CO)9(μ3-HBCO)] leads to decomposition. On the other hand, reaction of this dianionic complex with 2 equiv of FeCl3 gives a good yield of [Li][Fe3(CO)9(μ-CO)(μ3-HBCl). Metathesis with [AsPh4][Cl] yields [AsPh4][Fe3(CO)9(μ-CO)(μ3-HBCl)], which has been crystallographically characterized (triclinic, P1, a = 9.534(3) {\AA}, b = 13.305(4) {\AA}, c = 15.225(4) {\AA}, α = 104.39(2)°, β = 103.56(2)°, γ = 99.23(2)°, V = 1768.7(8) {\AA}3, Z = 2). Comparison with the analogous osmium clusters, as well as isoelectronic organometallic clusters, reveals relationships among their structures, properties, and energetics.",
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Synthesis of [AsPh4][Fe3(CO)9(μ-CO)(μ3-HBCl)] by Oxidative Chloride Substitution of [Fe3(CO)93-HBCO)]2-. / Crascall, Louise E.; Thimmappa, B. H.S.; Rheingold, Arnold L.; Ostrander, Robert; Fehlner, Thomas P.

In: Organometallics, Vol. 13, No. 6, 01.06.1994, p. 2153-2158.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis of [AsPh4][Fe3(CO)9(μ-CO)(μ3-HBCl)] by Oxidative Chloride Substitution of [Fe3(CO)9(μ3-HBCO)]2-

AU - Crascall, Louise E.

AU - Thimmappa, B. H.S.

AU - Rheingold, Arnold L.

AU - Ostrander, Robert

AU - Fehlner, Thomas P.

PY - 1994/6/1

Y1 - 1994/6/1

N2 - The deprotonation of (μ-H)Fe3(CO)9(μ-CO)(μ3-HBH) with n-butyllithium yields the dianionic complex [Li]2[Fe3(CO)9(μ3-HBCO)], which has been spectroscopically characterized. In contrast to the facile reprotonation of closely related ferraboranes, protonation of [Li]2[Fe3(CO)9(μ3-HBCO)] leads to decomposition. On the other hand, reaction of this dianionic complex with 2 equiv of FeCl3 gives a good yield of [Li][Fe3(CO)9(μ-CO)(μ3-HBCl). Metathesis with [AsPh4][Cl] yields [AsPh4][Fe3(CO)9(μ-CO)(μ3-HBCl)], which has been crystallographically characterized (triclinic, P1, a = 9.534(3) Å, b = 13.305(4) Å, c = 15.225(4) Å, α = 104.39(2)°, β = 103.56(2)°, γ = 99.23(2)°, V = 1768.7(8) Å3, Z = 2). Comparison with the analogous osmium clusters, as well as isoelectronic organometallic clusters, reveals relationships among their structures, properties, and energetics.

AB - The deprotonation of (μ-H)Fe3(CO)9(μ-CO)(μ3-HBH) with n-butyllithium yields the dianionic complex [Li]2[Fe3(CO)9(μ3-HBCO)], which has been spectroscopically characterized. In contrast to the facile reprotonation of closely related ferraboranes, protonation of [Li]2[Fe3(CO)9(μ3-HBCO)] leads to decomposition. On the other hand, reaction of this dianionic complex with 2 equiv of FeCl3 gives a good yield of [Li][Fe3(CO)9(μ-CO)(μ3-HBCl). Metathesis with [AsPh4][Cl] yields [AsPh4][Fe3(CO)9(μ-CO)(μ3-HBCl)], which has been crystallographically characterized (triclinic, P1, a = 9.534(3) Å, b = 13.305(4) Å, c = 15.225(4) Å, α = 104.39(2)°, β = 103.56(2)°, γ = 99.23(2)°, V = 1768.7(8) Å3, Z = 2). Comparison with the analogous osmium clusters, as well as isoelectronic organometallic clusters, reveals relationships among their structures, properties, and energetics.

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