N-(2-mercaptobenzyl)-N,N-bis(2-pyridylmethyl)amine | 217962-06-6

• 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-(2-mercaptobenzyl)-N,N-bis(2-pyridylmethyl)amine
• 英文别名: 2-({Bis[(pyridin-2-yl)methyl]amino}methyl)benzene-1-thiol；2-[[bis(pyridin-2-ylmethyl)amino]methyl]benzenethiol
• CAS: 217962-06-6
• 化学式: C₁₉H₁₉N₃S
• 分子量: 321.446
• InChiKey: FFBIKKILLDDRRZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.16
• 拓扑面积：
  30
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethylzinc 、 N-(2-mercaptobenzyl)-N,N-bis(2-pyridylmethyl)amine 以 正己烷 、 甲苯 为溶剂， 以77%的产率得到(2-Mercaptobenzyl-bis-(2-pyridylmethyl)amin)Zn-C2H5
  参考文献：
  名称：

  Zinkkomplexe des N,N,S-Liganden 2-Mercaptobenzyl-bis-(2-pyridylmethyl)amin

  摘要：

  An improved synthesis of the title ligand MBPA-H has made its complex chemistry accessible. With diethyl zinc it forms the reactive ethyl complex (MBPA)Zn-C2H5 (1) whose reaction with phenol leads to (MBPA)Zn-OC6H5 (2). With zinc nitrate the labile compound (MBPA)Zn-ONO2 (3) is formed which in turn is converted with thiophenolate into (MBPA)Zn-SC6H5 (4). Structure determinations of 2 and 3 have confirmed severely deformed trigonal-bipyramidal coordinations of the zinc atom whose ligation patterns correspond to those in some hydrolytic zinc enzymes.

  DOI：

  10.1002/1521-3749(200111)627:11<2523::aid-zaac2523>3.0.co;2-5
• 作为产物：
  描述：

  硫代水杨酸 在 manganese(IV) oxide 、 sodium tetrahydroborate 、 potassium tert-butylate 、 sodium hydride 、 sodium cyanoborohydride 、 溶剂黄146 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 116.0h， 生成 N-(2-mercaptobenzyl)-N,N-bis(2-pyridylmethyl)amine
  参考文献：
  名称：

  高自旋镍 (II) 配合物的顺磁 NMR 研究。双核与单核物种的受控合成、结构、电子和磁特性

  摘要：

  已合成具有不同 N/S 供体集的新不对称叔胺 (N(3)SR) 以提供单核和双核配合物。乙酸根离子用于完成围绕镍 (II) 原子的八面体配位球。可以控制单核系统向双核系统的轻松转化，以从同一配体产生单核或双核复合物。双核复合物 a(BPh(4))(2) ([Ni(2)(N(3)SSN(3))(OAc)(2)](BPh(4))(2))固态通过 X 射线衍射技术作为溶剂化物：a(BPh(4))(2).(1/2)[5(CH(3)OH).(CH(3)CN).(CH(3) )CH(2)OH)]。两个 Ni 原子是六配位的，并由一个二硫化物基团和两个双齿乙酸酯桥接。磁化率揭示了 J = 2.5(7) cm(-1) 的两个 Ni 原子之间的弱铁磁交换相互作用。UV-vis 研究表明六配位结构在溶液中持续存在。a(BPh(4))(2) 的 (1) H 核磁共振谱表现出明显的超精细移位配体信号。完整的共振分

  DOI：

  10.1021/ja010342k

文献信息

• Synthesis and characterization of molybdenum oxo complexes of two tripodal ligands: reactivity studies of a functional model for molybdenum oxotransferases
  作者：Anders Thapper、Axel Behrens、Jacob Fryxelius、Maria H. Johansson、Fabio Prestopino、Miklós Czaun、Dieter Rehder、Ebbe Nordlander

  DOI：10.1039/b505180k

  日期：——

  Reaction of the tetradentate ligand N-(2-hydroxybenzyl)-N,N-bis(2-pyridylmethyl)amine (L–OH) with MoO2Cl2 in methanol in the presence of NaOMe and PF6− results in the formation of [MoO2(L–O)]PF6. Similarly, the reaction of N-(2-mercaptobenzyl)-N,N-bis(2-pyridylmethyl)amine (L–SH) with MoO2(acac)2 leads to the formation of [MoO2(L–S)]+. The dioxo-molybdenum complex [MoO2(L–O)]+ reacts with phosphines in methanol to afford phosphine oxides and an air-sensitive molybdenum complex, tentatively identified as [Mo(IV)O(L–O)(OCH3)]. The latter complex is capable of reducing biological oxygen donors such as DMSO or nitrate, thereby mimicking the activity of DMSO reductase and nitrate reductase. Reaction of [MoO2(L–O)]PF6 with PPh3 in other solvents than methanol leads to the formation of the Mo(V) dimer [(L–O)OMo(μ-O)MoO(L–O)](PF6)2. The crystal structures of [MoO2(L–O)]PF6 and the μ-oxo bridged dimer are presented.

  四齿配体N-(2-羟基苄基)-N,N-bis(2-吡啶甲基)胺(L–OH)与MoO2Cl2在甲醇中，在NaOMe和PF6−的存在下反应，形成[MoO2(L–O)]PF6。类似地，N-(2-巯基苄基)-N,N-bis(2-吡啶甲基)胺(L–SH)与MoO2(acac)2的反应生成[MoO2(L–S)]⁺。二氧茂铝复合物[MoO2(L–O)]⁺在甲醇中与磷烯反应，生成磷烯氧化物和一个对空气敏感的铝复合物，暂时鉴定为[Mo(IV)O(L–O)(OCH3)]。后者复合物能够还原生物氧给体，如DMSO或硝酸盐，从而模拟DMSO还原酶和硝酸盐还原酶的活性。[MoO2(L–O)]PF6与PPh3在不同于甲醇的溶剂中反应形成Mo(V)二聚体[(L–O)OMo(μ-O)MoO(L–O)](PF6)2。提供了[MoO2(L–O)]PF6和μ-氧桥连二聚体的晶体结构。
• Engineering Coordination Environment of Cobalt Center in Molecular Catalysts for Improved Photocatalytic <scp>CO₂</scp> Reduction
  作者：Yuchen Wang、Jihong Zhang、Wei Yang、Weixue Tao、Keying Tao、Jihua Deng、Wenjie Shi、Dichang Zhong、Tongbu Lu

  DOI：10.1002/cjoc.202300378

  日期：2023.12

  inexpensive catalysts is essential for photocatalytic CO2 reduction. Homogeneous molecular catalysts, possessing definite crystal structures, are desirable to study the relationship between catalytic performance and coordination microenvironment around catalytic center. In this report, we elaborately developed three Co(II)-based molecular catalysts with different coordination microenvironments for CO2 reduction

  创造有效且廉价的催化剂对于光催化CO 2还原至关重要。均质分子催化剂具有确定的晶体结构，适合研究催化性能与催化中心周围配位微环境之间的关系。在本报告中，我们精心开发了三种具有不同配位微环境的CO 2还原Co(II)基分子催化剂，分别命名为[CoN 3 O]ClO 4、[CoN 4 ]ClO 4和[CoN 3 S]ClO 4，分别。最优的[CoN 3 O]ClO 4光催化剂光催化还原CO 2的最大TON为5652 ，分别是[CoN 4 ]ClO 4和[CoN 3 S]ClO 4的1.28和1.65倍。L 1 ( N , N-双(2-吡啶甲基)-N- ( 2-羟基苄基)胺)中氧的高电负性为Co(II)催化中心提供了低还原电位和更稳定的*COOH中间体，促进CO 2到CO的转化并解释[CoN 3 O]ClO 4的高光催化活性。这项工作为研究人员开发光催化CO 2还原催化剂提供了新的见解。
• Sulfinato Iron(III) Complex for Electrocatalytic Proton Reduction
  作者：Andrew C. Cavell、Carolyn L. Hartley、Dan Liu、Connor S. Tribble、William R. McNamara

  DOI：10.1021/ic5030394

  日期：2015.4.6

  We report the first example of a sulfinato Fe(III) complex acting as a highly active electrocatalyst for proton reduction. The sulfinate binds to the metal through oxygen, resulting in a seven-membered chelate ring that is likely hemilabile during catalysis. Proton reduction occurs at -1.57 V versus Fc/Fc(+) in CH3CN with an i(c)/i(p) = 13 in CH3CN (k(obs) = 3300 s(-1)) and an overpotential of 800 mV. The catalysis is first order with respect to [catalyst] and second order with respect to [trifluoracetic acid]. An 11% increase in catalytic activity is observed in the presence of water, suggesting that sulfinate moieties are viable functional groups for aqueous proton reduction catalysts.
• Paramagnetic NMR Investigations of High-Spin Nickel(II) Complexes. Controlled Synthesis, Structural, Electronic, and Magnetic Properties of Dinuclear vs Mononuclear Species
  作者：Catherine Belle、Catherine Bougault、Marie-Thérèse Averbuch、André Durif、Jean-Louis Pierre、Jean-Marc Latour、Laurent Le Pape

  DOI：10.1021/ja010342k

  日期：2001.8.1

  sphere around nickel(II) atom(s). The facile conversion of mononuclear to dinuclear systems can be controlled to produce either mono- or dinuclear complexes from the same ligand. The dinuclear complex a(BPh(4))(2) ([Ni(2)(N(3)SSN(3))(OAc)(2)](BPh(4))(2)) has been characterized in the solid state by X-ray diffraction techniques as solvate: a(BPh(4))(2).(1/2)[5(CH(3)OH).(CH(3)CN).(CH(3)CH(2)OH)]. The

  已合成具有不同 N/S 供体集的新不对称叔胺 (N(3)SR) 以提供单核和双核配合物。乙酸根离子用于完成围绕镍 (II) 原子的八面体配位球。可以控制单核系统向双核系统的轻松转化，以从同一配体产生单核或双核复合物。双核复合物 a(BPh(4))(2) ([Ni(2)(N(3)SSN(3))(OAc)(2)](BPh(4))(2))固态通过 X 射线衍射技术作为溶剂化物：a(BPh(4))(2).(1/2)[5(CH(3)OH).(CH(3)CN).(CH(3) )CH(2)OH)]。两个 Ni 原子是六配位的，并由一个二硫化物基团和两个双齿乙酸酯桥接。磁化率揭示了 J = 2.5(7) cm(-1) 的两个 Ni 原子之间的弱铁磁交换相互作用。UV-vis 研究表明六配位结构在溶液中持续存在。a(BPh(4))(2) 的 (1) H 核磁共振谱表现出明显的超精细移位配体信号。完整的共振分
• Zinkkomplexe des N,N,S-Liganden 2-Mercaptobenzyl-bis-(2-pyridylmethyl)amin
  作者：Alexander Trösch、Heinrich Vahrenkamp

  DOI：10.1002/1521-3749(200111)627:11<2523::aid-zaac2523>3.0.co;2-5

  日期：2001.11

  An improved synthesis of the title ligand MBPA-H has made its complex chemistry accessible. With diethyl zinc it forms the reactive ethyl complex (MBPA)Zn-C2H5 (1) whose reaction with phenol leads to (MBPA)Zn-OC6H5 (2). With zinc nitrate the labile compound (MBPA)Zn-ONO2 (3) is formed which in turn is converted with thiophenolate into (MBPA)Zn-SC6H5 (4). Structure determinations of 2 and 3 have confirmed severely deformed trigonal-bipyramidal coordinations of the zinc atom whose ligation patterns correspond to those in some hydrolytic zinc enzymes.