文摘
The Co(II) and Mn(II) complexes (tmeda)Co(ESiMe3)2 (E = S, 1a; E = Se, 1b), (3,5-Me2C5H3N)2Co(ESiMe3)2 (E = S, 2a; E = Se, 2b), [Li(tmeda)]2[(tmeda)Mn5(μ-ESiMe3)2(ESiMe3)4(μ4-E)(μ3-E)2] (E = S, 3a; E = Se, 3b), [Li(tmeda)]2[Mn(SSiMe3)4] (4), [Li(tmeda)]4[Mn4(SeSiMe3)4(μ3-Se)4] (5), and [Li(tmeda)]4[Mn(Se4)3] (6) (tmeda = N,N,N′,N′-tetramethylethylenediamine) have been isolated from reactions of Li[ESiMe3] and the chloride salts of these metals. The treatment of (tmeda)CoCl2 with two equivalents of Li[ESiMe3] (E = S, Se) yields 1a and 1b, respectively, whereas similar reactions with MnCl2 yield the polynuclear complexes 3a (E = S) and 3b (E = Se). The selective preparation of the mononuclear complex 4 is achieved by increasing the reaction ratios of Li[SSiMe3] to MnCl2 to 4:1. Single crystal X-ray analysis of complexes 1−5, confirms the presence of the trimethylsilylchalcogenolate moieties and distorted tetrahedral geometry around the metal centers in each of these complexes. The structure of the tris(tetraselenide) complex [Li(tmeda)]4[Mn(Se4)3] (6), isolated in small quantities from the preparation of 5, is also described.