Oxalate bridged heteronuclear compounds containing MM quadruple bonds (M = Mo and W) and their radical cations

Malcolm H. Chisholm; Nathan J. Patmore

doi:10.1139/V08-093

Oxalate bridged heteronuclear compounds containing MM quadruple bonds (M = Mo and W) and their radical cations

Malcolm H. Chisholm, Nathan J. Patmore

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6 Citations (Scopus)

Abstract

The heteronuclear MM quadruply bonded oxalate bridged compound [(t-BuCO₂)₃MoW]₂(μ-C₂O ₄) (I) has been prepared from the reaction between MoW(O ₂Ct-Bu)₄ and oxalic acid and characterized by elemental analysis, ¹H NMR and UV-vis spectroscopy, and electrochemical studies. Single electron oxidation of I by reaction with Ag⁺PF ₆^- leads to the formation of the kinetically labile radical cation I⁺, which has been characterized by UV-vis, NIR, and EPR spectroscopy. The latter results are compared with the properties of their related homonuclear Mo₄- and W₄-oxalate bridged compounds and their respective radical cations. The spectroscopic features of the related radical cations [(t-BuCO₂)₆Mo_xW _y(μ-C₂O₄)]⁺, where x = 1, 2, 3 and y = 4 - x, are also described with the conclusion that the [(t-BuCO ₂)₃Mo₂(μ-C₂O₄)W ₂(O₂Ct-Bu)₃]⁺ and [(t-BuCO ₂)₃Mo₂(μ-C₂O₄)MoW (O₂Ct-Bu)₃]⁺ cations are valence trapped on the Robin and Day scheme for the classification of mixed valence compounds.

Original language	English
Pages (from-to)	88-94
Number of pages	7
Journal	Canadian Journal of Chemistry
Volume	87
Issue number	1 SPEC. ISS.
DOIs	https://doi.org/10.1139/V08-093
Publication status	Published - 1 Jan 2009
Externally published	Yes

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@article{3a344669a008472896f53830ad95d5c3,

title = "Oxalate bridged heteronuclear compounds containing MM quadruple bonds (M = Mo and W) and their radical cations",

abstract = "The heteronuclear MM quadruply bonded oxalate bridged compound [(t-BuCO2)3MoW]2(μ-C2O 4) (I) has been prepared from the reaction between MoW(O 2Ct-Bu)4 and oxalic acid and characterized by elemental analysis, 1H NMR and UV-vis spectroscopy, and electrochemical studies. Single electron oxidation of I by reaction with Ag+PF 6- leads to the formation of the kinetically labile radical cation I+, which has been characterized by UV-vis, NIR, and EPR spectroscopy. The latter results are compared with the properties of their related homonuclear Mo4- and W4-oxalate bridged compounds and their respective radical cations. The spectroscopic features of the related radical cations [(t-BuCO2)6MoxW y(μ-C2O4)]+, where x = 1, 2, 3 and y = 4 - x, are also described with the conclusion that the [(t-BuCO 2)3Mo2(μ-C2O4)W 2(O2Ct-Bu)3]+ and [(t-BuCO 2)3Mo2(μ-C2O4)MoW (O2Ct-Bu)3]+ cations are valence trapped on the Robin and Day scheme for the classification of mixed valence compounds.",

keywords = "Mixed valence, Molybdenum, Tungsten",

author = "Chisholm, \{Malcolm H.\} and Patmore, \{Nathan J.\}",

year = "2009",

month = jan,

day = "1",

doi = "10.1139/V08-093",

language = "English",

volume = "87",

pages = "88--94",

journal = "Canadian Journal of Chemistry",

issn = "0008-4042",

publisher = "National Research Council of Canada",

number = "1 SPEC. ISS.",

}

TY - JOUR

T1 - Oxalate bridged heteronuclear compounds containing MM quadruple bonds (M = Mo and W) and their radical cations

AU - Chisholm, Malcolm H.

AU - Patmore, Nathan J.

PY - 2009/1/1

Y1 - 2009/1/1

N2 - The heteronuclear MM quadruply bonded oxalate bridged compound [(t-BuCO2)3MoW]2(μ-C2O 4) (I) has been prepared from the reaction between MoW(O 2Ct-Bu)4 and oxalic acid and characterized by elemental analysis, 1H NMR and UV-vis spectroscopy, and electrochemical studies. Single electron oxidation of I by reaction with Ag+PF 6- leads to the formation of the kinetically labile radical cation I+, which has been characterized by UV-vis, NIR, and EPR spectroscopy. The latter results are compared with the properties of their related homonuclear Mo4- and W4-oxalate bridged compounds and their respective radical cations. The spectroscopic features of the related radical cations [(t-BuCO2)6MoxW y(μ-C2O4)]+, where x = 1, 2, 3 and y = 4 - x, are also described with the conclusion that the [(t-BuCO 2)3Mo2(μ-C2O4)W 2(O2Ct-Bu)3]+ and [(t-BuCO 2)3Mo2(μ-C2O4)MoW (O2Ct-Bu)3]+ cations are valence trapped on the Robin and Day scheme for the classification of mixed valence compounds.

AB - The heteronuclear MM quadruply bonded oxalate bridged compound [(t-BuCO2)3MoW]2(μ-C2O 4) (I) has been prepared from the reaction between MoW(O 2Ct-Bu)4 and oxalic acid and characterized by elemental analysis, 1H NMR and UV-vis spectroscopy, and electrochemical studies. Single electron oxidation of I by reaction with Ag+PF 6- leads to the formation of the kinetically labile radical cation I+, which has been characterized by UV-vis, NIR, and EPR spectroscopy. The latter results are compared with the properties of their related homonuclear Mo4- and W4-oxalate bridged compounds and their respective radical cations. The spectroscopic features of the related radical cations [(t-BuCO2)6MoxW y(μ-C2O4)]+, where x = 1, 2, 3 and y = 4 - x, are also described with the conclusion that the [(t-BuCO 2)3Mo2(μ-C2O4)W 2(O2Ct-Bu)3]+ and [(t-BuCO 2)3Mo2(μ-C2O4)MoW (O2Ct-Bu)3]+ cations are valence trapped on the Robin and Day scheme for the classification of mixed valence compounds.

KW - Mixed valence

KW - Molybdenum

KW - Tungsten

UR - https://www.scopus.com/pages/publications/67650888657

U2 - 10.1139/V08-093

DO - 10.1139/V08-093

M3 - Article

AN - SCOPUS:67650888657

SN - 0008-4042

VL - 87

SP - 88

EP - 94

JO - Canadian Journal of Chemistry

JF - Canadian Journal of Chemistry

IS - 1 SPEC. ISS.

ER -

Oxalate bridged heteronuclear compounds containing MM quadruple bonds (M = Mo and W) and their radical cations

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