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

doi:10.1016/0022-328X(94)87184-1

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 journal › Article › peer-review

7 Citations (Scopus)

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 Pd^iI, 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 Pd^II-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 Fe^IIS 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 Fell^III/II couple. Although cyclic voltammetric waves for the Cu^II,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 language	English
Pages (from-to)	47-51
Number of pages	5
Journal	Journal of Organometallic Chemistry
Volume	484
Issue number	1-2
DOIs	https://doi.org/10.1016/0022-328X(94)87184-1
Publication status	Published - 1994 Dec 27
Externally published	Yes

Keywords

Copper
Electrochemistry
Ferrocenophanes
Iron
Palladium

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/0022-328X(94)87184-1

Cite this

@article{3eefdef3e3ee450891c1bb97868420b5,

title = "Redox reactivity of azathiaferrocenophane complexes with copper(II) and palladium(II)",

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.",

keywords = "Copper, Electrochemistry, Ferrocenophanes, Iron, Palladium",

author = "Kim, {Jong Seung} and Bessire, {Andrew J.} and Bartsch, {Richard A.} and Holwerda, {Robert A.} and Czech, {Bronislaw P.}",

note = "Funding Information: We thank the Welch Foundation for financial support of this researcht hrough Grants D-735 (R.A.H.) and D-775 (R.A.B.).",

year = "1994",

month = dec,

day = "27",

doi = "10.1016/0022-328X(94)87184-1",

language = "English",

volume = "484",

pages = "47--51",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "1-2",

}

TY - JOUR

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.

N1 - Funding Information: We thank the Welch Foundation for financial support of this researcht hrough Grants D-735 (R.A.H.) and D-775 (R.A.B.).

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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U2 - 10.1016/0022-328X(94)87184-1

DO - 10.1016/0022-328X(94)87184-1

M3 - Article

AN - SCOPUS:0002002179

SN - 0022-328X

VL - 484

SP - 47

EP - 51

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -

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

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