N,N'-dimethyl-N,N'-bis(2-S-mercaptophenyl)ethylenediamine | 109334-45-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯硫酚类
• 英文名称: N,N'-dimethyl-N,N'-bis(2-S-mercaptophenyl)ethylenediamine
• 英文别名: 1,2-ethanediamine-N,N'-dimethyl-N,N'-bis(2-benzenethiol)；N,N'-dimethyl-N,N'-bis(2-mercaptophenyl)ethylenediamine；Benzenethiol, 2,2'-[1,2-ethanediylbis(methylimino)]bis-；2-[methyl-[2-(N-methyl-2-sulfanylanilino)ethyl]amino]benzenethiol
• CAS: 109334-45-4
• 化学式: C₁₆H₂₀N₂S₂
• 分子量: 304.48
• InChiKey: VJWZMJMBRUMSAY-UHFFFAOYSA-N

物化性质

• 沸点：
  447.4±40.0 °C(Predicted)
• 密度：
  1.210±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  8.5
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  {RuCl2(NCMe)4} 、 N,N'-dimethyl-N,N'-bis(2-S-mercaptophenyl)ethylenediamine 在 LiOCH₃ 作用下， 以 甲醇 为溶剂， 生成 [Ru(1,2-ethanediamine-N,N'-dimethyl-N,N'-bis(2-benzenethiolato))(SC6H4NMeCH2CH2NHMeC6H4S-κ2S2)]
  参考文献：
  名称：

  Phosphane effects on formation and reactivity of [Ru(L)(PR3)(`N2Me2S2')] complexes with L=N2, N2H4, NH3, and CO

  摘要：

  Metal-sulfur complex fragments, to which small molecules like N-2, N2H2, N2H4, NH3, or CO can bind, are desirable model compounds concerning enzymatic N-2 fixation.This paper reports on the effects of the phosphane co-ligand on formation and reactivity of [Ru(L)(PR3)('N2Me2S2')] ['N2Me2S2'(2-) = 1,2-ethanediamine-N,N'-dimethyl-N,N'-bis(2-benzenethiolate)(2-)] complexes with nitrogenase relevant ligands, especially N-2, N2H4, NH3, and CO.Treatment of [Ru(NCCH3)(4)Cl-2] with Li-2'N2Me2S2', excessive LiOMe, bulky PPh3 or PCy3, respectively, led to the formation of two series of [Ru(L)(PR3)('N2Me2S2')1 complexes [for R = Ph: 1b, 1c (L = NCCH3 6b (L = N2H4), 7b (L = N-2) 8b(1-3) (L = CO), 9b (L = NH3); for R = Cy: 1a (L = NCCH3), 6a (L = N2H4), 7a(L = N-2), 8a (L = CO), 9a (L = NH3)]. While the use of PPh3 (theta = 145degrees) yielded cis,trans and cis,cis isomers of [Ru(NCCH3)(PPh3)('N2Me2S2')] (1b, 1c), no isomer formation was observed with the bulkier phosphane PCy3 (theta = 170degrees). Sterically less demanding phosphanes (theta = 118-132degrees) afforded bisphosphane complexes [Ru(PR3)(2)('N2Me2S2')] [2d (R = Me), 2e (R = Et), 2f (R = nPr), and 2g (R = nBu)], which were practically inert and could only be converted in two cases and under drastic reaction conditions into the CO complexes [Ru(CO)(PR3)('N2Me2S2')] [4e (R=Et), 4f (R = nPr)]. The chelating bidentate phosphane dppe (bisdiphenylphosphanoethane) yielded exclusively the mononuclear complex [Ru(dppe)('N2Me2S2')] (3). (C) 2004 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2004.03.014
• 作为产物：
  描述：

  2-(甲基氨基)苯硫酚 在 sodium hydroxide 、 sodium 、 sodium cyanoborohydride 、 zinc(II) chloride 、 正丁醇 作用下， 以 乙醇 、 水 、 正丁醇 为溶剂， 反应 15.0h， 生成 N,N'-dimethyl-N,N'-bis(2-S-mercaptophenyl)ethylenediamine
  参考文献：
  名称：

  Molybdenum(VI) and molybdenum(V) complexes with N,N'-dimethyl-N,N'-bis(2-mercaptophenyl)ethylenediamine. Electrochemical and electron paramagnetic resonance models for the molybdenum(VI/V) centers of the molybdenum hydroxylases and related enzymes

  摘要：

  DOI：

  10.1021/ja00253a016

文献信息

• Übergangsmetallkomplexe mit Schwefelliganden, CXXXIII [1]. Synthese, Struktur und Eigenschaften neuer Fe^II-Komplexe mit [FeN₂S₂]-Gerüsten / Transition Metal Complexes with Sulfur Ligands, CXXXIII [1]. Synthesis, Structure, and Properties of New Fe^II Complexes with [Fe₂N₂S₂] Cores
  作者：Dieter Sellmann、Susanne Emig、Frank W. Heinemann、Falk Knoch

  DOI：10.1515/znb-1998-1208

  日期：1998.12.1

  (2), Pr (3), Bu (4)), [Fe(PMe3)2 (′N2H2S2′)] (7), [Fe(dppe)(′N2H2S2′)] (8 , dppe = 1,2- bis(diphenylphosphine)ethane), and [Fe(P(ÖR)3)2(′N2H2S2′)l (R = Me (9), Pr (10)). Mixed phosphane/phosphite complexes [Fe(PMe3)(P(OR)3)(′N2H2S2′)] (R = Me (11), Pr (12)) were synthesized by PMe3/P(OPr)3 exchange of the labile complexes [Fe(PMe3 )2(′N2H2S2′)] (7) and [Fe(P(OPr)3)2(′N2H2S2′)] (10). The [Fe(CO)(PR3)(′N2H2S2′)l

  摘要 为了获得模拟固氮酶活性位点反应性的铁配合物的合适前体，系统研究了 [Fe('N2H2S2')] 片段的配位化学('N2H2S2'2- = 1,2-乙二胺-N,N'-双(2-苯硫醇盐)(2-))。FeCl2 -4H2O 与四齿胺硫醇配体 'N2H2S2'2- 和 CO、PR3 或 P(OR)3 的一锅反应生成复合物 [Fe(CO)2('N2H2S2')] (1), [ Fe(CO)(PR3)('N2H2S2')] (R = Et (2), Pr (3), Bu (4)), [Fe(PMe3)2 ('N2H2S2')] (7), [Fe (dppe)('N2H2S2')] (8 , dppe = 1,2-双(二苯基膦)乙烷), 和 [Fe(P(ÖR)3)2('N2H2S2')l (R = Me (9), Pr (10))。混合磷烷/亚磷酸盐配合物 [Fe(PMe3)(P(OR)3)('N2H2S2')]
• Sellmann, Dieter; Ruf, Richard; Knoch, Falk, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1995, vol. 50, # 5, p. 791 - 801
  作者：Sellmann, Dieter、Ruf, Richard、Knoch, Falk、Moll, Matthias

  DOI：——

  日期：——
• [Ru(N2)(PiPr3)(`N2Me2S2')]: Coordination of Molecular N2 to Metal Thiolate Cores under Mild Conditions
  作者：Dieter Sellmann、Barbara Hautsch、Annette Rösler、Frank W. Heinemann

  DOI：10.1002/1521-3773(20010417)40:8<1505::aid-anie1505>3.0.co;2-2

  日期：2001.4.17

  N2 coordination to the nitrogenase Fe7 MoS9 cofactor is considered a key step of biological N2 fixation, however, modeling this step with metal-sulfur complex fragments under mild conditions has remained a long-standing challenge. The title complex 2 represents a first example, forming from N2 and the precursor CH3 CN complex 1 under standard conditions [Eq. (1)].
• Syntheses and structures of four- and five-coordinate bio-related zinc complexes containing dithiolate–diamine ligands
  作者：Shaban Y. Shaban

  DOI：10.1016/j.ica.2010.11.042

  日期：2011.2

  Two new zinc complexes, namely, [Zn(N2H2S2)}(2)] (3) [N2H2S22 = N,N-bis(2-mercaptophenyl)ethylendiamine (2-)] and [Zn(N2Me2S2)] (4) [N2Me2S22 = N,N'-dimethyl-N,N'-bis(2-mercaptophenyl)ethylendiamine) (2-)] have been synthesized and structurally characterized by X-ray structure analyses. The structure of 3 consists of a bis(mu-thiolato) binuclear unit, in which each zinc center was found to reside in an N2S3 array between square-pyramidal and trigonal-bipyramidal environment. The two zinc centers are bridged by one of the two thiolates of an [N2S2] ligand. In the crystal packing, the neighboring binuclear units interact with each other by H-bonding interaction, which extends the binuclear unit into a 3D network. In contrast to 3 complex 4 is mononuclear, where each zinc center now was found to reside in an N2S2 distorted tetrahedral environment with a large S-Zn-S bite angle. The relevance of these compounds in biological systems is discussed. Unlike 3, the formation of hydrogen bridges in 4 is no longer possible and instead the molecular packing is determined by p-stacking between the phenyl rings. (C) 2010 Elsevier B.V. All rights reserved.
• Mononuclear and Binuclear Molybdenum(V) Complexes of the Ligand <i>N</i>,<i>N</i>‘-Dimethyl-<i>N</i>,<i>N</i>‘-bis(2-mercaptophenyl)ethylenediamine:  Geometric Isomers
  作者：Keith R. Barnard、Michael Bruck、Susan Huber、Carina Grittini、John H. Enemark、Robert W. Gable、Anthony G. Wedd

  DOI：10.1021/ic960848h

  日期：1997.2.12

  The syntheses of mononuclear complexes cis-Mo(V)OXL (X = Cl, Br, OMe, OEt, OPh, SPh, NCS, OSiMe(3)) and two binuclear complexes Mo(2)(V)O(3)L(2) of the title ligand LH(2) are reported. Two forms of MoOCIL, with cis oxo and chloro ligands, were crystallized, one in space group P2(1)/n, with a 10.440(2) Angstrom, b = 14.260(2) Angstrom, 12.041(2) Angstrom, beta = 102.76(2)degrees, V = 1748(1) Angstrom(3), and Z = 4, and the other in P2(1)/n, with a = 13.564(4) Angstrom, b = 7.172(2) Angstrom, c = 18.242(6) Angstrom, beta = 95.19(1)degrees, V = 1767(2) Angstrom(3), and Z = 4. MoO(OSiMe(3))L crystallizes in space group P2(1)/c, with a = 15.923(3) Angstrom, b = 11.141(2) Angstrom, c = 14.186(2) Angstrom, beta = 112.64(2)degrees, V = 2323(1) Angstrom(3), and Z = 4, while MoO(NCS)L crystallizes in Pna2(1), with a = 22.471(2) Angstrom, b = 12.136(2) Angstrom, c = 7.138(1) Angstrom, V = 1947(1) Angstrom(3), and Z = 4. The four structures reveal two possible conformations for ligand L: one with trans S atoms (cis,trans-MoOCIL and -MoO(OSiMe(3))L) and one with cis S atoms (cis,cis-MoOCIL and -MoO(NCS)L). The cis, cis isomers are converted to the cis,trans forms under reflux in MeCN at 80 degrees C. Only the cis,trans forms could be isolated for bulkier ligands X (OPh, SPh, OSiMe(3)). A short H3C ... X interaction is present in the cis,cis forms: C ... Cl = 3.07 Angstrom and C ... N = 2.93 Angstrom, for X = Cl and NCS, respectively. Infrared and electronic spectral data provide unambiguous identification of the stereochemistry of ligand L in mononuclear complexes MoOXL. Effective removal of ligand X = OR from cis,cis-MoO(OR)L (R = Me, Et) led to two binuclear complexes (Mo(V)OL)(2)(mu-O) of C-i and C-1 point symmetries. C-i-(MoOL)(2)(mu-O). thf crystallizes in space group P2(1)/c, with a = 8.5650(5) Angstrom, b = 15.1862(9) Angstrom, c = 16.8038(9) Angstrom, beta = 100.183(1)Alpha, V = 2157.1(8) Angstrom(3), and Z = 2, while C-1-(MoOL)(2)(mu-O). CH2Cl2 crystallizes in space group P2(1)/c, with a = 12.5250(5) Angstrom, b = 24.673(1) Angstrom, c = 12.7253(6) Angstrom, beta = 108.070(4)degrees, V = 3738.6(3) Angstrom(3), and Z = 4. C-i-(MoOL)(2)(mu-O). thf features two cis,trans-Mo(V)OXL centers with X = mu-O, while C-1-(MoOL)(2)(mu-O). CH2Cl2 contains a cis,trapls and a cis,cis center. In the latter, the Mo-O-Mo link is asymmetric, allowing relief of steric crowding on the cis,cis side of the molecule.