lithium 2,6-dimesitylphenyl thiolate | 182625-30-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: lithium 2,6-dimesitylphenyl thiolate
• 英文别名: Lithium;2,6-bis(2,4,6-trimethylphenyl)benzenethiolate；lithium;2,6-bis(2,4,6-trimethylphenyl)benzenethiolate
• CAS: 182625-30-5
• 化学式: C₂₄H₂₅S*Li
• 分子量: 352.47
• InChiKey: YLXINPJZAVLFCZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.78
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  lithium 2,6-dimesitylphenyl thiolate 在 二氯硅烷 作用下， 以 5,5-dimethyl-1,3-cyclohexadiene 、 乙醚 、 甲苯 为溶剂， 以99%的产率得到
  参考文献：
  名称：

  Isolation of a Stable, Acyclic, Two-Coordinate Silylene

  摘要：

  The synthesis and characterization of a stable, acyclic two-coordinate silylene, Si(SArMe6)(2) [Ar-Me6 = C6H3-2,6(C6H2-2,4,6-Me-3)(2)], by reduction of Br2Si(SArMe6) 2 with a magnesium(I) reductant is described. It features a V-shaped silicon coordination with a S-Si-S angle of 90.52(2)degrees and an average Si-S distance of 2.158(3) angstrom. Although it reacts readily with an alkyl halide, it does not react with hydrogen under ambient conditions, probably as a result of the ca. 4.3 eV energy difference between the frontier silicon lone pair and 3p orbitals.

  DOI：

  10.1021/ja301091v

文献信息

• Dispersion Forces and Counterintuitive Steric Effects in Main Group Molecules: Heavier Group 14 (Si–Pb) Dichalcogenolate Carbene Analogues with Sub-90° Interligand Bond Angles
  作者：Brian D. Rekken、Thomas M. Brown、James C. Fettinger、Felicitas Lips、Heikki M. Tuononen、Rolfe H. Herber、Philip P. Power

  DOI：10.1021/ja403802a

  日期：2013.7.10

  The synthesis and spectroscopic and structural characterization of an extensive series of acyclic, monomeric tetrylene dichalcogenolates of formula M(ChAr)2 (M = Si, Ge, Sn, Pb; Ch = O, S, or Se; Ar = bulky m-terphenyl ligand, including two new acyclic silylenes) are described. They were found to possess several unusual features-the most notable of which is their strong tendency to display acute interligand

  式 M(ChAr)2（M = Si、Ge、Sn、Pb；Ch = O、S 或 Se；Ar = 大三联苯配体，包括两个新的无环亚甲硅烷）进行了描述。发现它们具有几个不寻常的特征——其中最显着的是它们强烈倾向于显示锐角配位体，Ch-M-Ch，键角通常远低于 90°。此外，与正常的立体预期相反，发现配体间的角度随着配体尺寸的增加而变窄。实验和结构数据与高级 DFT 计算相结合，包括对色散效应的校正，得出的结论是色散力在稳定它们的锐角配位方面起着重要作用。
• Stable Plumbylene Dichalcogenolate Monomers with Large Differences in Their Interligand Angles and the Synthesis and Characterization of a Monothiolato Pb(II) Bromide and Lithium Trithiolato Plumbate
  作者：Brian D. Rekken、Thomas M. Brown、Marilyn M. Olmstead、James C. Fettinger、Philip P. Power

  DOI：10.1021/ic302513c

  日期：2013.3.18

  metathesis routes and represent the first fully characterized monomeric, two-coordinate, lead dichalcogenolates in the solid state. Structural studies showed that the S–Pb–S angle (77.21(4)°) is about 22° narrower than the corresponding O–Pb–O angle. 207Pb NMR and electronic spectroscopy show that the separation between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital

  络合物Pb（ChAr Pri 4）2（Ch = O（1），S（2）; Ar Pri 4 = C 6 H 3 -2,6-（C 6 H 3 -2,6-Pr i 2）2）是通过醇解和盐复分解途径合成的，代表了固态的第一个完全表征的单体，二配位，二卤化二氢四氢萘酸铅。结构研究表明，S–Pb–S角（77.21（4）°）比相应的O–Pb–O角窄约22°。207Pb NMR和电子光谱表明，最高占据分子轨道（HOMO）和最低未占据分子轨道（LUMO）之间的距离从双芳基氧亚plum基变为双硫代巯基衍生物。LiSAr的反应我6与PbBr 2以2：1比例的LED不与Pb（SAR我6）2，但要的monothiolato铅的混合物（II）络合物，铅（BR）（μ-SAR我6） } 2（3）和三硫代铅酸锂锂LiPb（SAr Me 6）3（4）。3和4 通过分级重结晶分离并纯化，并通过X射线晶体学和光谱学研究对两者进行表征。
• Effects of Remote Ligand Substituents on the Structures, Spectroscopic, and Magnetic Properties of Two-Coordinate Transition-Metal Thiolate Complexes
  作者：Jade Pratt、Aimee M. Bryan、Michelle Faust、Jessica N. Boynton、Petra Vasko、Brian D. Rekken、Akseli Mansikkamäki、James C. Fettinger、Heikki M. Tuononen、Philip P. Power

  DOI：10.1021/acs.inorgchem.8b00551

  日期：2018.6.4

  62058(9) Å (5), and 1.724(8) Å (6). However, the d5 (Mn) and d10 (Zn) complexes 3 and 7 display linear or near-linear coordination with no close metal–ligand distances. The nonlinear geometries of 1 and 4–6 also contrast with those of their AriPr4-substituted alkoxo and amido congeners, which have strictly linear coordination. Complexes 1–7 were synthesized by the reaction of the lithium or sodium thiolate

  第一行过渡金属（II）二硫醇盐M（SAr iPr 4）2 [Ar iPr 4 = C 6 H 3 -2,6-（C 6 H 3 -2,6-iPr 2）2；M = Cr（1），Mn（3），Fe（4），Co（5），Ni（6）和Zn（7）]和Cr（SAr Me 6）2 [ 2 ; Ar Me 6 = C 6 H 3 -2,6-（C 6 H 2描述了-2,4,6-Me 3）2 ]和配体转移试剂（NaSAr iPr 4）2（8）。与它们的M（SAr iPr 6）2（M = Cr，Mn，Fe，Co，Ni和Zn; Ar iPr 6 = C 6 H 3 -2,6-（C 6 H 2 -2,4， 6-的iPr 3）2）同系物，这不同于1和3 - 6在具有p上的三联苯取代基的侧翼芳基环-异丙基，化合物1和4 - 6使用S-M-S显示高度弯曲协调的几何形状的角度109.802（2）°（1），120.2828（3）°（4），91
• Reversible Heterolysis of H₂ Mediated by an M−S(Thiolate) Bond (M = Ir, Rh): A Mechanistic Implication for [NiFe] Hydrogenase
  作者：Yasuhiro Ohki、Mayumi Sakamoto、Kazuyuki Tatsumi

  DOI：10.1021/ja804848w

  日期：2008.9.3

  Facile H-2 heterolysis was found to be mediated by coordinatively unsaturated Cp*Ir and Cp*Rh thiolate complexes. The reaction of iridium complex is reversible, and the formation of an intermediary Ir-H/thiol complex was detected. The reversible conversion between thiolate complex+H-2 and hydride complex+thiol provides an intriguing functional model of [NiFe] hydrogenase.
• Synthesis and characterization of sterically encumbered aluminum thiolato complexes with rare Al/S/halide structural motifs
  作者：Felicitas Lips、James C. Fettinger、Philip P. Power

  DOI：10.1016/j.poly.2014.04.056

  日期：2014.9

  The reaction of the bulky lithium terphenyl thiolates LISArMe6 (Ar-Me6 = C6H3-2,6-(C6H2-2,4,6-Me-3)(2)) and LiSAriPr4 (AriPr4 = C8H3-2,6-(C8H3-2,6-iPr2)2) with AlBr3 in PhMe or Et20 resulted in the formation of two new lithium aluminum thiolate salts LiAl(SArme6)2Br2.PhMe 1, [LiAl(SArme6)Br312 2, and the etherate Al(SAriPr4)13r2(OEt2) 3. Compounds 1-3 were structurally characterized and analyzed by 1H, 13C NMR and IR spectroscopy. In further investigations the reduction of 1 and 2 with KC8 or Rieke's magnesium in different solvent systems afforded the compounds KAI(SArme6)3H.2PhMe 4 and LiAl(SArme6)Bro3811.84(2THF).PhMe 5. All of the compounds described herein contain four-coordinate aluminum atoms with distorted tetrahedral geometries. (C) 2014 Elsevier Ltd. All rights reserved.