Redox reactivity of azathiaferrocenophane complexes with copper(II) and palladium(II)

Jong Seung Kim, Andrew J. Bessire, Richard A. Bartsch, Robert A. Holwerda, Bronislaw P. Czech

Research output: Contribution to journalArticle

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Abstract

To further probe the influence of coordinated metal ions on the electrochemical behavior of azathiaferrocenophane ligands, a series of palladium(II) and copper(II) complexes with both cyclic and acyclic ferrocenophanes has been prepared, spectroscopically characterized and examined by cyclic voltammetry. New complexes of N,N-didecyl-2,8-diaza-5-thia[9](1,1′) ferrocenophane (1) are [1]HPd(CH3CN)(BF4)3, [1]Pd(PPh3)2(BF4)2 · CH2Cl2, [1]Pd(AsPh3)2 (BF4)2 · 1.5CH2Cl2, [1]Pd(C6O4Cl2) · (HN(C2H5)3)2(BF4)2 · H2O and [1]H2Pd(bpy)(BF4)4. Copper(II) compounds reported include [2]Cu(CH3CO2)2 · 2H2O (2 = 1,5-bis(ferrocenyl)-3-thia-1,5-diaminopentane), [3]Cu(CH3CO2)2 (3 = 1,8-bis(ferrocenyl)-3,6-dithia-1,8 -diaminooctane) and Cu(bas)(CH3CO2)2 (bas = 3-thia-1,5-diaminopentane). The [1]HPd(CH3CN)3+ ca tion (E 1 2(F by tridentate S2N ferrocenophane ligation, leaving one coordination position open to the CH3CN ligand and a protonated aza nitrogen atom uncoordinated. In contrast, 1 ligates PdiI, only through its pair of thioether sulfur atoms in [1]Pd(PPh3)22+ (E 1 2 = 0.58 V) and [1]Pd(AsPh3)22+ (E 1 2 = 0.59 V). The PdII-chloranilate interaction in [1]Pd(C6O4Cl2) · (HN(C2H5)3)2(BF4)2 · H2O is too weak to disrupt ferrocenophane tridentate chelation or to restore the FeIIS bonding previously documented for [1]Pd(C6O4Cl2), which was prepared by another synthetic route. Electronic spectra of [2]Cu(CH3CO2)2 · 2H2O and [3 ]Cu(CH3CO2)2 are consistent with tridentate S2N and tetradentate S2N2 ligat ion of Cu II, respectively, and a finding of E 1 2 = 0.48 V for both complexes is in accord with expectations for the electrostatic influence of a bivalent cation on the FellIII/II couple. Although cyclic voltammetric waves for the CuII,I couple were not observed, the redox reactivity of [2]Cu2+ towards reduction was evaluated through a kinetic study of electron transfer within its mercaptoacetate adduct.

Original languageEnglish
Pages (from-to)47-51
Number of pages5
JournalJournal of Organometallic Chemistry
Volume484
Issue number1-2
Publication statusPublished - 1994 Dec 27
Externally publishedYes

Fingerprint

Palladium
Oxidation-Reduction
palladium
Copper
reactivity
Ligands
Copper compounds
Ions
copper
Atoms
ligands
chelation
Sulfides
Chelation
Static Electricity
Sulfur
electronic spectra
nitrogen atoms
adducts
Cyclic voltammetry

Keywords

  • Copper
  • Electrochemistry
  • Ferrocenophanes
  • Iron
  • Palladium

ASJC Scopus subject areas

  • Biochemistry
  • Chemical Engineering (miscellaneous)
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Science (miscellaneous)
  • Materials Chemistry

Cite this

Kim, J. S., Bessire, A. J., Bartsch, R. A., Holwerda, R. A., & Czech, B. P. (1994). Redox reactivity of azathiaferrocenophane complexes with copper(II) and palladium(II). Journal of Organometallic Chemistry, 484(1-2), 47-51.

Redox reactivity of azathiaferrocenophane complexes with copper(II) and palladium(II). / Kim, Jong Seung; Bessire, Andrew J.; Bartsch, Richard A.; Holwerda, Robert A.; Czech, Bronislaw P.

In: Journal of Organometallic Chemistry, Vol. 484, No. 1-2, 27.12.1994, p. 47-51.

Research output: Contribution to journalArticle

Kim, JS, Bessire, AJ, Bartsch, RA, Holwerda, RA & Czech, BP 1994, 'Redox reactivity of azathiaferrocenophane complexes with copper(II) and palladium(II)', Journal of Organometallic Chemistry, vol. 484, no. 1-2, pp. 47-51.
Kim, Jong Seung ; Bessire, Andrew J. ; Bartsch, Richard A. ; Holwerda, Robert A. ; Czech, Bronislaw P. / Redox reactivity of azathiaferrocenophane complexes with copper(II) and palladium(II). In: Journal of Organometallic Chemistry. 1994 ; Vol. 484, No. 1-2. pp. 47-51.
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T1 - Redox reactivity of azathiaferrocenophane complexes with copper(II) and palladium(II)

AU - Kim, Jong Seung

AU - Bessire, Andrew J.

AU - Bartsch, Richard A.

AU - Holwerda, Robert A.

AU - Czech, Bronislaw P.

PY - 1994/12/27

Y1 - 1994/12/27

N2 - To further probe the influence of coordinated metal ions on the electrochemical behavior of azathiaferrocenophane ligands, a series of palladium(II) and copper(II) complexes with both cyclic and acyclic ferrocenophanes has been prepared, spectroscopically characterized and examined by cyclic voltammetry. New complexes of N,N-didecyl-2,8-diaza-5-thia[9](1,1′) ferrocenophane (1) are [1]HPd(CH3CN)(BF4)3, [1]Pd(PPh3)2(BF4)2 · CH2Cl2, [1]Pd(AsPh3)2 (BF4)2 · 1.5CH2Cl2, [1]Pd(C6O4Cl2) · (HN(C2H5)3)2(BF4)2 · H2O and [1]H2Pd(bpy)(BF4)4. Copper(II) compounds reported include [2]Cu(CH3CO2)2 · 2H2O (2 = 1,5-bis(ferrocenyl)-3-thia-1,5-diaminopentane), [3]Cu(CH3CO2)2 (3 = 1,8-bis(ferrocenyl)-3,6-dithia-1,8 -diaminooctane) and Cu(bas)(CH3CO2)2 (bas = 3-thia-1,5-diaminopentane). The [1]HPd(CH3CN)3+ ca tion (E 1 2(F by tridentate S2N ferrocenophane ligation, leaving one coordination position open to the CH3CN ligand and a protonated aza nitrogen atom uncoordinated. In contrast, 1 ligates PdiI, only through its pair of thioether sulfur atoms in [1]Pd(PPh3)22+ (E 1 2 = 0.58 V) and [1]Pd(AsPh3)22+ (E 1 2 = 0.59 V). The PdII-chloranilate interaction in [1]Pd(C6O4Cl2) · (HN(C2H5)3)2(BF4)2 · H2O is too weak to disrupt ferrocenophane tridentate chelation or to restore the FeIIS bonding previously documented for [1]Pd(C6O4Cl2), which was prepared by another synthetic route. Electronic spectra of [2]Cu(CH3CO2)2 · 2H2O and [3 ]Cu(CH3CO2)2 are consistent with tridentate S2N and tetradentate S2N2 ligat ion of Cu II, respectively, and a finding of E 1 2 = 0.48 V for both complexes is in accord with expectations for the electrostatic influence of a bivalent cation on the FellIII/II couple. Although cyclic voltammetric waves for the CuII,I couple were not observed, the redox reactivity of [2]Cu2+ towards reduction was evaluated through a kinetic study of electron transfer within its mercaptoacetate adduct.

AB - To further probe the influence of coordinated metal ions on the electrochemical behavior of azathiaferrocenophane ligands, a series of palladium(II) and copper(II) complexes with both cyclic and acyclic ferrocenophanes has been prepared, spectroscopically characterized and examined by cyclic voltammetry. New complexes of N,N-didecyl-2,8-diaza-5-thia[9](1,1′) ferrocenophane (1) are [1]HPd(CH3CN)(BF4)3, [1]Pd(PPh3)2(BF4)2 · CH2Cl2, [1]Pd(AsPh3)2 (BF4)2 · 1.5CH2Cl2, [1]Pd(C6O4Cl2) · (HN(C2H5)3)2(BF4)2 · H2O and [1]H2Pd(bpy)(BF4)4. Copper(II) compounds reported include [2]Cu(CH3CO2)2 · 2H2O (2 = 1,5-bis(ferrocenyl)-3-thia-1,5-diaminopentane), [3]Cu(CH3CO2)2 (3 = 1,8-bis(ferrocenyl)-3,6-dithia-1,8 -diaminooctane) and Cu(bas)(CH3CO2)2 (bas = 3-thia-1,5-diaminopentane). The [1]HPd(CH3CN)3+ ca tion (E 1 2(F by tridentate S2N ferrocenophane ligation, leaving one coordination position open to the CH3CN ligand and a protonated aza nitrogen atom uncoordinated. In contrast, 1 ligates PdiI, only through its pair of thioether sulfur atoms in [1]Pd(PPh3)22+ (E 1 2 = 0.58 V) and [1]Pd(AsPh3)22+ (E 1 2 = 0.59 V). The PdII-chloranilate interaction in [1]Pd(C6O4Cl2) · (HN(C2H5)3)2(BF4)2 · H2O is too weak to disrupt ferrocenophane tridentate chelation or to restore the FeIIS bonding previously documented for [1]Pd(C6O4Cl2), which was prepared by another synthetic route. Electronic spectra of [2]Cu(CH3CO2)2 · 2H2O and [3 ]Cu(CH3CO2)2 are consistent with tridentate S2N and tetradentate S2N2 ligat ion of Cu II, respectively, and a finding of E 1 2 = 0.48 V for both complexes is in accord with expectations for the electrostatic influence of a bivalent cation on the FellIII/II couple. Although cyclic voltammetric waves for the CuII,I couple were not observed, the redox reactivity of [2]Cu2+ towards reduction was evaluated through a kinetic study of electron transfer within its mercaptoacetate adduct.

KW - Copper

KW - Electrochemistry

KW - Ferrocenophanes

KW - Iron

KW - Palladium

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