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 - http://www.scopus.com/inward/record.url?scp=67650888657&partnerID=8YFLogxK
U2 - 10.1139/V08-093
DO - 10.1139/V08-093
M3 - Article
AN - SCOPUS:67650888657
VL - 87
SP - 88
EP - 94
JO - Canadian Journal of Chemistry
JF - Canadian Journal of Chemistry
SN - 0008-4042
IS - 1 SPEC. ISS.
ER -