Department of Chemistry, The University of Western Ontario, London, Ontario, N6A 5B7 Canada.
Inorg Chem. 2010 Aug 16;49(16):7289-97. doi: 10.1021/ic902346u.
The Co(II) and Mn(II) complexes (tmeda)Co(ESiMe(3))(2) (E = S, 1a; E = Se, 1b), (3,5-Me(2)C(5)H(3)N)(2)Co(ESiMe(3))(2) (E = S, 2a; E = Se, 2b), Li(tmeda)[(tmeda)Mn(5)(mu-ESiMe(3))(2)(ESiMe(3))(4)(mu(4)-E)(mu(3)-E)(2)] (E = S, 3a; E = Se, 3b), Li(tmeda)[Mn(SSiMe(3))(4)] (4), [Li(tmeda)]4[Mn(4)(SeSiMe(3))(4)(mu(3)-Se)(4)] (5), and Li(tmeda)[Mn(Se(4))(3)] (6) (tmeda = N,N,N',N'-tetramethylethylenediamine) have been isolated from reactions of Li[ESiMe(3)] and the chloride salts of these metals. The treatment of (tmeda)CoCl(2) with two equivalents of Li[ESiMe(3)] (E = S, Se) yields 1a and 1b, respectively, whereas similar reactions with MnCl(2) 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[SSiMe(3)] to MnCl(2) 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)[Mn(Se(4))(3)] (6), isolated in small quantities from the preparation of 5, is also described.
已从锂[ESiMe₃]与这些金属的氯化物盐的反应中分离出钴（II）和锰（II）配合物（tmeda）Co（ESiMe(₃)）₂（E = S，1a；E = Se，1b）、（3,5-Me₂C₅H₃N）₂Co（ESiMe(₃)）₂（E = S，2a；E = Se，2b）、[Li（tmeda）]₂[（tmeda）Mn₅（μ - ESiMe(₃)）₂（ESiMe(₃)）₄（μ₄ - E）（μ₃ - E）₂]（E = S，3a；E = Se，3b）、[Li（tmeda）]₂[Mn（SSiMe(₃)）₄]（4）、[Li（tmeda）]₄[Mn₄（SeSiMe(₃)）₄（μ₃ - Se）₄]（5）和[Li（tmeda）]₄[Mn（Se₄）₃]（6）（tmeda = N，N，N′，N′ - 四甲基乙二胺）。用两当量的锂[ESiMe₃]（E = S，Se）处理（tmeda）CoCl₂分别得到1a和1b，而与MnCl₂的类似反应得到多核配合物3a（E = S）和3b（E = Se）。通过将锂[SSiMe₃]与MnCl₂的反应比例增加到4∶1，可选择性地制备单核配合物4。配合物1 - 5的单晶X射线分析证实了这些配合物中每个配合物的金属中心周围均存在三甲基硅基硫属醇盐部分以及扭曲的四面体几何结构。还描述了从5的制备中少量分离出的三（四硒化物）配合物[Li（tmeda）]₄[Mn（Se₄）₃]（6）的结构。
