Institut für Anorganische Chemie der Universität Göttingen, Tammannstrasse 4, 37077 Göttingen, Germany.
Inorg Chem. 2010 Mar 15;49(6):2743-9. doi: 10.1021/ic902071m.
Three new diimidosulfinates, TMSCH(2)S(N(t)Bu)(2)Li (1), 2-PyCH(2)S(N(t)Bu)(2)Li (2), and [{PhCH(2)S(N(t)Bu)(2)Li}(2) x THF] (3) (TMS = trimethylsilyl; Py = 2-pyridyl), have been synthesized by the reaction of functionalized alpha-CH(2)-organolithium compounds with bis-tert-butylsulfurdiimide. These new organolithium chelates are characterized by NMR ((1)H, (13)C, (7)Li, and (29)Si) spectroscopy and single-crystal X-ray diffraction analyses. Compounds 1 and 2 crystallize as dimers without donor molecules, whereas one of the lithium atoms in 3 is coordinated by a single THF molecule. The crystal structure of 1 shows significant intramolecular proximity between one methyl group of the trimethylsilyl (TMS) and one lithium atom, which could be described as an electrostatic Li...C interaction. The coordination sphere of each lithium atom in 2 is completed by donation from the nitrogen atom of the pyridyl ring; however, one of the lithium atoms in 3 is coordinated by a THF molecule. In addition, the first mixed sulfurdiimide species containing a diimidosulfinate and a diimidosulfite fragment, [{PhCHS(N(t)Bu)(2)Li(2)(THF)(2)}{MeS(N(t)Bu)(2)Li(THF)}] (4), was isolated by deprotonation of the alpha-CH(2) group in 3. The single-crystal X-ray structure of 4 revealed two different S-bound substituents coexisting in one dimer and two asymmetrically coordinated lithium atoms.
三种新的二亚胺二硫代氨基甲酸盐，TMSCH(2)S(N(t)Bu)(2)Li (1)，2-PyCH(2)S(N(t)Bu)(2)Li (2)和[{PhCH(2)S(N(t)Bu)(2)Li}(2) x THF] (3) (TMS = 三甲基硅基; Py = 2-吡啶基)，是通过功能化的α-CH(2)-有机锂化合物与双叔丁基硫代二亚胺反应合成的。这些新的有机锂配合物通过 NMR ((1)H、(13)C、(7)Li 和 (29)Si)光谱和单晶 X 射线衍射分析进行了表征。化合物 1 和 2 结晶为没有给体分子的二聚体，而 3 中的一个锂原子被单个 THF 分子配位。1 的晶体结构显示出三甲基硅基 (TMS) 的一个甲基和一个锂原子之间存在显著的分子内接近，这可以被描述为静电 Li...C 相互作用。2 中每个锂原子的配位球由吡啶环上的氮原子提供;然而，3 中的一个锂原子被一个 THF 分子配位。此外，通过 3 中α-CH(2)基团的去质子化分离出了第一个含有二亚胺二硫代氨基甲酸盐和二亚胺亚磺酸盐片段的混合硫代二亚胺物种，[{PhCHS(N(t)Bu)(2)Li(2)(THF)(2)}{MeS(N(t)Bu)(2)Li(THF)}] (4)。4 的单晶 X 射线结构揭示了两个不同的 S 键取代基共存于一个二聚体中，以及两个不对称配位的锂原子。
