Resonance Raman Investigation of Equatorial Ligand Donor Effects on the Cu2O22+ Core in End-On and Side-On μ-Peroxo-Dicopper (II) and Bis-μ-oxo-Dicopper (III) …

…, HC Liang, KD Karlin, EI Solomon

Index: Henson, Mark J.; Vance, Michael A.; Zhang, Christiana Xin; Hong-Chang, Liang; Karlin, Kenneth D.; Solomon, Edward I. Journal of the American Chemical Society, 2003 , vol. 125, # 17 p. 5186 - 5192

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Citation Number: 70

Abstract

The effect of endogenous donor strength on Cu2O2 bonds was studied by electronically perturbing [{(R-TMPA) CuII} 2 (O2)] 2+ and [{(R-MePY2) Cu} 2 (O2)] 2+(R= H, MeO, Me2N), which form the end-on μ-1, 2 bound peroxide and an equilibrium mixture of side-on peroxo- dicopper (II) and bis-μ-oxo-dicopper (III) isomers, respectively. For [{(R-TMPA) CuII} 2 (O2)] 2+, νO-O shifts from 827 to 822 to 812 cm-1 and νCu-O (sym) shifts from 561 to 557 to 551 ...