Catalysis of the electroreduction of O2 to H2O by vanadium-salen complexes in acidified dichloromethane

Eishun Tsuchida; Kenichi Oyaizu; Eniya Listiani Dewi; Takahiro Imai; Fred C. Anson

doi:10.1021/ic990268v

Catalysis of the electroreduction of O₂ to H₂O by vanadium-salen complexes in acidified dichloromethane

Eishun Tsuchida^*, Kenichi Oyaizu, Eniya Listiani Dewi, Takahiro Imai, Fred C. Anson

^*Corresponding author for this work

School of Advanced Science and Engineering

Research output: Contribution to journal › Article › peer-review

55 Citations (Scopus)

Abstract

Addition of stoichiometric quantities of trifluoromethanesulfonic (triflic) acid to solutions of V^IVO(salen) (H₂-salen = N,N′-ethylenebis(salicylideneamine)) in dichloromethane produces the μ-oxo dinuclear vanadium(IV) complex [(salen)V^IVOV^IV(salen)]²⁺ ([V^IVOV^IV]²⁺). Addition of significant excesses of triflic acid converts the dimer into [V^IV(salen)]²⁺. In dichloromethane solutions containing 0.1 M tetrabutylammonium tetrafluoroborate, the [V^IVOV^IV]²⁺ complex undergoes disproportionation and dissociation reactions to produce a solution containing an equimolar mixture of V^IVO(salen), [V^III(salen)]⁺, and [V^IVOV^V]³⁺. The oxophilic [V^III(salen)]⁺ complex reacts with O₂ to accomplish a four-electron reduction of O₂: 2[V^III(salen)]⁺ + O₂ → 2[V^VO(salen)]⁺. These reactions can be exploited to carry out catalytic electroreductions of O₂ to H₂O in acidified dichloromethane solutions of V^IVO(salen) at unusually positive potentials.

Original language	English
Pages (from-to)	3704-3708
Number of pages	5
Journal	Inorganic Chemistry
Volume	38
Issue number	16
DOIs	https://doi.org/10.1021/ic990268v
Publication status	Published - 1999

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/ic990268v

Cite this

@article{aa0df3a3e981402085ae2ff43190240c,

title = "Catalysis of the electroreduction of O2 to H2O by vanadium-salen complexes in acidified dichloromethane",

abstract = "Addition of stoichiometric quantities of trifluoromethanesulfonic (triflic) acid to solutions of VIVO(salen) (H2-salen = N,N′-ethylenebis(salicylideneamine)) in dichloromethane produces the μ-oxo dinuclear vanadium(IV) complex [(salen)VIVOVIV(salen)]2+ ([VIVOVIV]2+). Addition of significant excesses of triflic acid converts the dimer into [VIV(salen)]2+. In dichloromethane solutions containing 0.1 M tetrabutylammonium tetrafluoroborate, the [VIVOVIV]2+ complex undergoes disproportionation and dissociation reactions to produce a solution containing an equimolar mixture of VIVO(salen), [VIII(salen)]+, and [VIVOVV]3+. The oxophilic [VIII(salen)]+ complex reacts with O2 to accomplish a four-electron reduction of O2: 2[VIII(salen)]+ + O2 → 2[VVO(salen)]+. These reactions can be exploited to carry out catalytic electroreductions of O2 to H2O in acidified dichloromethane solutions of VIVO(salen) at unusually positive potentials.",

author = "Eishun Tsuchida and Kenichi Oyaizu and Dewi, {Eniya Listiani} and Takahiro Imai and Anson, {Fred C.}",

year = "1999",

doi = "10.1021/ic990268v",

language = "English",

volume = "38",

pages = "3704--3708",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "16",

}

TY - JOUR

T1 - Catalysis of the electroreduction of O2 to H2O by vanadium-salen complexes in acidified dichloromethane

AU - Tsuchida, Eishun

AU - Oyaizu, Kenichi

AU - Dewi, Eniya Listiani

AU - Imai, Takahiro

AU - Anson, Fred C.

PY - 1999

Y1 - 1999

N2 - Addition of stoichiometric quantities of trifluoromethanesulfonic (triflic) acid to solutions of VIVO(salen) (H2-salen = N,N′-ethylenebis(salicylideneamine)) in dichloromethane produces the μ-oxo dinuclear vanadium(IV) complex [(salen)VIVOVIV(salen)]2+ ([VIVOVIV]2+). Addition of significant excesses of triflic acid converts the dimer into [VIV(salen)]2+. In dichloromethane solutions containing 0.1 M tetrabutylammonium tetrafluoroborate, the [VIVOVIV]2+ complex undergoes disproportionation and dissociation reactions to produce a solution containing an equimolar mixture of VIVO(salen), [VIII(salen)]+, and [VIVOVV]3+. The oxophilic [VIII(salen)]+ complex reacts with O2 to accomplish a four-electron reduction of O2: 2[VIII(salen)]+ + O2 → 2[VVO(salen)]+. These reactions can be exploited to carry out catalytic electroreductions of O2 to H2O in acidified dichloromethane solutions of VIVO(salen) at unusually positive potentials.

AB - Addition of stoichiometric quantities of trifluoromethanesulfonic (triflic) acid to solutions of VIVO(salen) (H2-salen = N,N′-ethylenebis(salicylideneamine)) in dichloromethane produces the μ-oxo dinuclear vanadium(IV) complex [(salen)VIVOVIV(salen)]2+ ([VIVOVIV]2+). Addition of significant excesses of triflic acid converts the dimer into [VIV(salen)]2+. In dichloromethane solutions containing 0.1 M tetrabutylammonium tetrafluoroborate, the [VIVOVIV]2+ complex undergoes disproportionation and dissociation reactions to produce a solution containing an equimolar mixture of VIVO(salen), [VIII(salen)]+, and [VIVOVV]3+. The oxophilic [VIII(salen)]+ complex reacts with O2 to accomplish a four-electron reduction of O2: 2[VIII(salen)]+ + O2 → 2[VVO(salen)]+. These reactions can be exploited to carry out catalytic electroreductions of O2 to H2O in acidified dichloromethane solutions of VIVO(salen) at unusually positive potentials.

UR - http://www.scopus.com/inward/record.url?scp=0000572567&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000572567&partnerID=8YFLogxK

U2 - 10.1021/ic990268v

DO - 10.1021/ic990268v

M3 - Article

AN - SCOPUS:0000572567

SN - 0020-1669

VL - 38

SP - 3704

EP - 3708

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 16

ER -

Catalysis of the electroreduction of O₂ to H₂O by vanadium-salen complexes in acidified dichloromethane

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this