Synthesis and Reactivity of $\mu$-$\eta^{2}$:$\eta^{2}$-Disulfido Dicopper(II) Complex with N,N$\aku '$,N$\aku''$-Trimethyl-1,3,5-cis,cis-triaminocyclohexane

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A new $\mu$-$\eta^{2}$:$\eta^{2}$-disulfido dicopper(II) complex (1) was prepared from the reaction of copper(I) complex with N,N$\aku '$,N$\aku''$-trimethyl-1,3,5-cis,cis-triaminocyclohexane (R3TACH; $\text{R}=\text{Me}$) and elemental sulfur at room temperature in CH2Cl2. The UV--visible spectrum of 1 gave four peaks at 353 ($\varepsilon = 18300$), 397 ($\varepsilon = 10000$), 462 ($\varepsilon = 6000$), and 666 ($\varepsilon = 760$ M-1$\cdot$cm-1) nm in CH2Cl2, whose spectral pattern is similar to those of copper(II) complexes with other R3TACH derivatives [$\text{R}=\text{Et}$ (ethyl), iBu (isobutyl), and Bn (benzyl)] reported previously. The compound 1 was quite stable in the solid state, while in CH2Cl2, it was decomposed at 25 °C; the decomposition rate and half-lifetime were estimated to be $1.15\times 10^{-2}$ min-1 and 60 min, respectively. The stability was similar to that of the copper complex of Et3TACH, although it was lower than those of the disulfido dicopper(II) complexes with other TACH ligands. The compound 1 showed an oxidation reactivity toward triphenylphosphine to give triphenylphosphine sulfide with 68% yield. The relationship between the structures and oxidation reactivities of the $\mu$-$\eta^{2}$:$\eta^{2}$-disulfido dicopper(II) complexes were discussed in relation to the distortion around the Cu2S2 core and the steric hindrance between the substituent groups.
2011-01-25