Thiostannate tin-tin bond formation in solution: in situ generation of the mixed-valent, functionalized complex [{(RSn(IV))2(mu-S)2}3Sn(III)2S6].

In broad daylight: The double-decker thiostannate [(RSn(IV))(4)S(6)] (1, R = CMe(2)CH(2)COMe) condenses to form [{(RSn(IV))(2)(mu-S)(2)}(3)Sn(III)(2)S(6)] (2; see picture). This mixed-valent complex, which formally contains both Sn(III) and Sn(IV) atoms as confirmed by Mössbauer spectroscopy and DFT calculations, forms by a complicated, concerted mechanism. Additionally, 2 provides six carbonyl groups for further derivatization.