First crystal structure determination and high-frequency EPR study of an organoarsanecopper radical complex

, , , , , , , und . Inorganic Chemistry Communications 6 (9): 1196--1200 (2003)


The red radical complex (μ-bptz)Cu(AsPh3)22(BF4) 1, bptz = 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine, was obtained as a stable species and characterized by x-ray crystallog., spectroelectrochem. and EPR at 9.5 and 285 GHz. Comparison with the previously reported (μ-bptz)Cu(PPh3)22(BF4) 2 reveals longer Cu-element bonds by $\sim$0.1 \AA but otherwise a similar org. sandwich structure involving intramol. p(phenyl)-p(tetrazine)-p(phenyl) interactions, a 3+1 coordination at the Cu(I) centers, and averaged tetrazine intraring bond distances. Reversible oxidn. to a blue dication with an intense MLCT band at 650 nm occurs at -0.24 V vs. Fc+/0. EPR studies show the effect of the higher spin-orbit coupling const. of the As vs. P atoms through slightly larger g anisotropy as detd. through high frequency measurements. on SciFinder(R)

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