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

Malcolm H. Chisholm, Nathan J. Patmore

Research output: Contribution to journalArticle

5 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)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.

Original languageEnglish
Pages (from-to)88-94
Number of pages7
JournalCanadian Journal of Chemistry
Volume87
Issue number1 SPEC. ISS.
DOIs
Publication statusPublished - 1 Jan 2009
Externally publishedYes

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Bridged-Ring Compounds
Oxalates
Cations
Positive ions
Oxalic Acid
Oxalic acid
Ultraviolet spectroscopy
Paramagnetic resonance
Nuclear magnetic resonance
Spectroscopy
Oxidation
Electrons
Chemical analysis

Cite this

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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.",
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Oxalate bridged heteronuclear compounds containing MM quadruple bonds (M = Mo and W) and their radical cations. / Chisholm, Malcolm H.; Patmore, Nathan J.

In: Canadian Journal of Chemistry, Vol. 87, No. 1 SPEC. ISS., 01.01.2009, p. 88-94.

Research output: Contribution to journalArticle

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AU - Chisholm, Malcolm H.

AU - Patmore, Nathan J.

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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

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