Heterocubane cluster compounds (NEt4)Y:M(μ3-S)Re(CO)33(μ3-E) (M = W or Mo, Y = O or S, E = S or Se). Structures, spectroscopy, and electrochemistry

, , , , und . Zeitschrift fuer Anorganische und Allgemeine Chemie 627 (10): 2430--2444 (2001)


Thiometalates MS42- (M = Mo, W) or WOS32- react with Re(CO)5(O3SCF3) and Li2E (E = S or Se) to yield the following compds. which were structurally characterized: (NEt4)S:W(μ3-S)Re(CO)33(μ3-S)(NEt4) (I), (NEt4)O/S:W(μ3-S)Re(CO)3(μ3-S)(NEt4) (I/II), (mixed crystals), (NEt4)S:W(μ3-S)Re(CO)33(μ3-Se)(NEt4) (III) and (NEt4)S:Mo(μ3-S)Re(CO)33(μ3-S)(NEt4) (IV). The heterocubane anions I-IV contain electron-rich centers such as Re(I) or sulfide whereas Mo(VI) or W(VI) act as acceptor sites. Accordingly, the absorption spectra show long-wavelength metal-to-ligand charge transfer transitions, and cyclic voltammetry reveals a quasi-reversible redn. of the clusters. Although both 6-coordinate Re(I) and 4-coordinate metal(VI) centers are present in the clusters there is no evidence for significant metal-to-metal charge transfer interaction. on SciFinder(R)

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