Structural and electrochemical studies of dicupric Wells-Dawson sandwich-type complexes

Travis M. Anderson; Xikui Fang; Israel Martyr Mbomekalle; Bineta Keita; Louis Nadjo; Kenneth I. Hardcastle; Alireza Farsidjani; Craig L. Hill

doi:10.1007/s10876-006-0047-z

Structural and electrochemical studies of dicupric Wells-Dawson sandwich-type complexes

Travis M. Anderson
, Xikui Fang
, Israel Martyr Mbomekalle
, Bineta Keita
, Louis Nadjo
, Kenneth I. Hardcastle
, Alireza Farsidjani
, Craig L. Hill^*

^*Corresponding author for this work

Emory University
Bâtiment 350
City University of New York

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

21 Scopus citations

Abstract

A new Wells-Dawson sandwich polyoxometalate, αααα- [(NaOH₂)₂(Cu^II)₂ (P ₂W₁₅O₅₆)₂]^18- (2P), has been obtained in good yield by the dissolution of solid α-Na ₁₂[P₂W₁₅O₅₆]·18H ₂O in an aqueous solution of Cu(II) and L-glutamic acid at pH 10. The arsenic analogue, αααα-[(NaOH₂) ₂(Cu^II)₂(As₂W₁₅O ₅₆)₂]^18- (2As), is likewise prepared by using Na₁₂[As₂W₁₅O₅₆]·21H ₂O instead of Na₁₂[P₂W₁₅O ₅₆]·18H₂O. Diffraction quality crystals of both 2P and 2As were obtained by slow evaporation in air over several days. The X-ray structures of 2P and 2As reveal that two Cu(II) atoms are sandwiched between two α-[P₂W₁₅O₅₆]^12- or two α-[As₂W₁₅O₅₆]^12- ligands, respectively, while the other two positions of the central belt unit are occupied by two Na⁺ cations. Higher yields of 2As can be obtained by mixing CuCl₂·2H₂O and α[Na ₁₂As₂W₁₅O₅₆]·21H ₂O in acetate buffer. The electrochemistry of 2P and 2As is characterized by cyclic voltammograms in which the reduction of the Cu(II) centers is close to the redox pattern of the W-centers. The two Cu(II)-centers are simultaneously reduced to Cu(0); the separate steps could not be resolved for the individual Cu(II) centers. Complexes 2P and 2As constitute the second example, after αααα-[(NaOH₂) ₂(Fe^III)₂(P₂W₁₅O ₅₆)₂]^16- (1P) and αααα- [(NaOH₂)₂(Fe^III)₂(As ₂W₁₅O₅₆)₂]^16- (1As), of a transition-metal-substituted sandwich polyoxometalate containing two electroactive d-electron metals.

Original language	English
Pages (from-to)	183-195
Number of pages	13
Journal	Journal of Cluster Science
Volume	17
Issue number	2
DOIs	https://doi.org/10.1007/s10876-006-0047-z
State	Published - Jun 2006
Externally published	Yes

Keywords

Copper
Diarsenotungstates
Diphosphotungstates
Electrochemistry
Polyoxometalates
X-ray structure analysis

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10.1007/s10876-006-0047-z

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@article{6668f46d91d24341b71c12c6d854c4fe,

title = "Structural and electrochemical studies of dicupric Wells-Dawson sandwich-type complexes",

abstract = "A new Wells-Dawson sandwich polyoxometalate, αααα- [(NaOH2)2(CuII)2 (P 2W15O56)2]18- (2P), has been obtained in good yield by the dissolution of solid α-Na 12[P2W15O56]·18H 2O in an aqueous solution of Cu(II) and L-glutamic acid at pH 10. The arsenic analogue, αααα-[(NaOH2) 2(CuII)2(As2W15O 56)2]18- (2As), is likewise prepared by using Na12[As2W15O56]·21H 2O instead of Na12[P2W15O 56]·18H2O. Diffraction quality crystals of both 2P and 2As were obtained by slow evaporation in air over several days. The X-ray structures of 2P and 2As reveal that two Cu(II) atoms are sandwiched between two α-[P2W15O56]12- or two α-[As2W15O56]12- ligands, respectively, while the other two positions of the central belt unit are occupied by two Na+ cations. Higher yields of 2As can be obtained by mixing CuCl2·2H2O and α[Na 12As2W15O56]·21H 2O in acetate buffer. The electrochemistry of 2P and 2As is characterized by cyclic voltammograms in which the reduction of the Cu(II) centers is close to the redox pattern of the W-centers. The two Cu(II)-centers are simultaneously reduced to Cu(0); the separate steps could not be resolved for the individual Cu(II) centers. Complexes 2P and 2As constitute the second example, after αααα-[(NaOH2) 2(FeIII)2(P2W15O 56)2]16- (1P) and αααα- [(NaOH2)2(FeIII)2(As 2W15O56)2]16- (1As), of a transition-metal-substituted sandwich polyoxometalate containing two electroactive d-electron metals.",

keywords = "Copper, Diarsenotungstates, Diphosphotungstates, Electrochemistry, Polyoxometalates, X-ray structure analysis",

author = "Anderson, \{Travis M.\} and Xikui Fang and Mbomekalle, \{Israel Martyr\} and Bineta Keita and Louis Nadjo and Hardcastle, \{Kenneth I.\} and Alireza Farsidjani and Hill, \{Craig L.\}",

year = "2006",

month = jun,

doi = "10.1007/s10876-006-0047-z",

language = "英语",

volume = "17",

pages = "183--195",

journal = "Journal of Cluster Science",

issn = "1040-7278",

publisher = "Springer New York",

number = "2",

}

TY - JOUR

T1 - Structural and electrochemical studies of dicupric Wells-Dawson sandwich-type complexes

AU - Anderson, Travis M.

AU - Fang, Xikui

AU - Mbomekalle, Israel Martyr

AU - Keita, Bineta

AU - Nadjo, Louis

AU - Hardcastle, Kenneth I.

AU - Farsidjani, Alireza

AU - Hill, Craig L.

PY - 2006/6

Y1 - 2006/6

N2 - A new Wells-Dawson sandwich polyoxometalate, αααα- [(NaOH2)2(CuII)2 (P 2W15O56)2]18- (2P), has been obtained in good yield by the dissolution of solid α-Na 12[P2W15O56]·18H 2O in an aqueous solution of Cu(II) and L-glutamic acid at pH 10. The arsenic analogue, αααα-[(NaOH2) 2(CuII)2(As2W15O 56)2]18- (2As), is likewise prepared by using Na12[As2W15O56]·21H 2O instead of Na12[P2W15O 56]·18H2O. Diffraction quality crystals of both 2P and 2As were obtained by slow evaporation in air over several days. The X-ray structures of 2P and 2As reveal that two Cu(II) atoms are sandwiched between two α-[P2W15O56]12- or two α-[As2W15O56]12- ligands, respectively, while the other two positions of the central belt unit are occupied by two Na+ cations. Higher yields of 2As can be obtained by mixing CuCl2·2H2O and α[Na 12As2W15O56]·21H 2O in acetate buffer. The electrochemistry of 2P and 2As is characterized by cyclic voltammograms in which the reduction of the Cu(II) centers is close to the redox pattern of the W-centers. The two Cu(II)-centers are simultaneously reduced to Cu(0); the separate steps could not be resolved for the individual Cu(II) centers. Complexes 2P and 2As constitute the second example, after αααα-[(NaOH2) 2(FeIII)2(P2W15O 56)2]16- (1P) and αααα- [(NaOH2)2(FeIII)2(As 2W15O56)2]16- (1As), of a transition-metal-substituted sandwich polyoxometalate containing two electroactive d-electron metals.

AB - A new Wells-Dawson sandwich polyoxometalate, αααα- [(NaOH2)2(CuII)2 (P 2W15O56)2]18- (2P), has been obtained in good yield by the dissolution of solid α-Na 12[P2W15O56]·18H 2O in an aqueous solution of Cu(II) and L-glutamic acid at pH 10. The arsenic analogue, αααα-[(NaOH2) 2(CuII)2(As2W15O 56)2]18- (2As), is likewise prepared by using Na12[As2W15O56]·21H 2O instead of Na12[P2W15O 56]·18H2O. Diffraction quality crystals of both 2P and 2As were obtained by slow evaporation in air over several days. The X-ray structures of 2P and 2As reveal that two Cu(II) atoms are sandwiched between two α-[P2W15O56]12- or two α-[As2W15O56]12- ligands, respectively, while the other two positions of the central belt unit are occupied by two Na+ cations. Higher yields of 2As can be obtained by mixing CuCl2·2H2O and α[Na 12As2W15O56]·21H 2O in acetate buffer. The electrochemistry of 2P and 2As is characterized by cyclic voltammograms in which the reduction of the Cu(II) centers is close to the redox pattern of the W-centers. The two Cu(II)-centers are simultaneously reduced to Cu(0); the separate steps could not be resolved for the individual Cu(II) centers. Complexes 2P and 2As constitute the second example, after αααα-[(NaOH2) 2(FeIII)2(P2W15O 56)2]16- (1P) and αααα- [(NaOH2)2(FeIII)2(As 2W15O56)2]16- (1As), of a transition-metal-substituted sandwich polyoxometalate containing two electroactive d-electron metals.

KW - Copper

KW - Diarsenotungstates

KW - Diphosphotungstates

KW - Electrochemistry

KW - Polyoxometalates

KW - X-ray structure analysis

UR - https://www.scopus.com/pages/publications/33751516729

U2 - 10.1007/s10876-006-0047-z

DO - 10.1007/s10876-006-0047-z

M3 - 文章

AN - SCOPUS:33751516729

SN - 1040-7278

VL - 17

SP - 183

EP - 195

JO - Journal of Cluster Science

JF - Journal of Cluster Science

IS - 2

ER -

Structural and electrochemical studies of dicupric Wells-Dawson sandwich-type complexes

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Keywords

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