[(Ph2P(o-C6H4)S)2Ni] | 14897-21-3

• 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: [(Ph2P(o-C6H4)S)2Ni]
• 英文别名: bis(2-diphenylphosphanyl)thiophenolato[P,S]nickel；2-diphenylphosphanylbenzenethiolate;nickel(2+)
• CAS: 14897-21-3；138917-09-6
• 化学式: C₃₆H₂₈NiP₂S₂
• 分子量: 645.388
• InChiKey: GTQZTCSMMVBMTM-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  8.0
• 重原子数：
  41.0
• 可旋转键数：
  4.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  三甲基膦 、 tetrakis(trimethylphosphine)nickel(0) 、 [(Ph2P(o-C6H4)S)2Ni] 以 四氢呋喃 为溶剂， 以12%的产率得到(2-diphenylphosphanyl)-2-thionaphtholato[P,S]bis(trimethylphosphine)nickel
  参考文献：
  名称：

  Syntheses and properties of molecular nickel(II) hydride, methyl, and nickel(I) complexes supported by trimethylphosphane and (2-diphenylphosphanyl)thiophenolato and -naphtholato ligands

  摘要：

  2-Diphenylphosphanyl) thiophenol (PpSH) or (3-diphenylphosphanyl)-2-thionaphthol (PnSH) react with Ni(PMe3)(4) to form NiH(PpS)(PMe3)(2) (1) or NiH(PnS)(PMe3)(2) (2). 1,3-Bis(diphenylphosphanyl) propane (PP) replaces the monodentate phosphane ligands to give NiH(PpS)(PP) (3). NiMe(OMe)(PMe3) or NiMe2(PMe3)(3) react with PpSH to form NiMe(PpS)(PM3) (4) and NiMe( PpS)( PMe3)(2) (5), respectively, and PnSH affords NiMe(PnS)(PMe3)(2) (6), NiMe(PnS)(PMe3) (7). Dissociation of PMe3 ligands induces transformation of 1 to Ni(PpS)(PMe3)(2) (8) and Ni(PpS)(2). Crystal and molecular structures are given for 1, 5- 8, and dynamic solution spectra (NMR, EPR) are discussed. (C) 2009 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2009.01.023
• 作为产物：
  描述：

  o-(diphenylphosphino)thioanisole 在 Na/Hg amalgam 作用下， 以 四氢呋喃 、 丙醇 、 乙腈 为溶剂， 生成 [(Ph2P(o-C6H4)S)2Ni]
  参考文献：
  名称：

  膦基硫醚配合物中镍(0)、镍(I)和镍(II)的特征：(Ph2P(o-C6H4)SCH3)2Ni0的分子结构和S-脱烷基化

  摘要：

  镍 (0) 配合物与 P,S 供体原子配体的分子结构已通过 X 射线晶体学表征。配合物 1，(Ph2P(o-C6H4)SCH3)2Ni0，由 NiII 配合物 [(Ph2P(o-C6H4)SCH3)2Ni](BF4)2 ([2](BF4)2) 的 Na/Hg 汞齐还原制备, 光化学降解，失去 CH3 自由基，产生配合物 3，(Ph2P(o-C6H4)S)2NiII。三种化合物的晶体学参数如下： 1、单斜空间群 C2/c，a = 11.467(2) A, b = 17.613(3) A, c = 15.733(2) A, β = 96.450(10)° , V = 3157.5(9) A3，Z = 4；[2](BF4)2, 单斜空间群 P21/c，a = 9.417(4) A, b = 14.822(9) A, c = 13.773(2) A, β = 98.55(3)°, V = 9101

  DOI：

  10.1021/ja953686h
• 作为试剂：
  描述：

  盐酸 在 [(Ph2P(o-C6H4)S)2Ni] 作用下， 以 二氯甲烷 、 水 为溶剂， 生成 氢气
  参考文献：
  名称：

  Ni(PS)2 配合物的电催化析氢和氢氧化

  摘要：

  采用 PS 螯合物 2-(二苯基膦基) 苯硫醇 (HL1) 和 2-(二异丙基膦基) 苯硫醇 (HL2) 的四配位 Ni(II) 和 Zn(II) 配合物已被合成，并通过光谱、结构和电化学方法进行表征。筛选所有配合物的电催化活性，用于在三乙胺存在下与乙酸和盐酸一起析氢和氢气氧化。镍配合物 Ni(L1)2 (1) 被发现从外部酸中还原质子，以 140 s-1 的周转频率在 1.09 V 的过电位下生成氢，并使用氧化还原活性碱三乙胺 (Et3N) 与在 0.33 V 的过电位下，周转频率为 23 s-1。Ni(L2)2 (3) 也被发现是二氢氧化的活性催化剂，但由于在电位窗口中无法还原 Ni (II/I)，因此质子还原效率低下。发现 Zn(L1)2 (2) 和 Zn(L2)2 (4) 配合物对于它们对这两种反应的电催化行为是不够的。

  DOI：

  10.1002/ejic.201700590

文献信息

• Transmetallation reactions of [Sn(R)2(Ph2PC6H4-2-S)2] with metal complexes of the Group 10
  作者：Daniel Canseco-González、Valente Gómez-Benı́tez、Simón Hernández-Ortega、Rubén A Toscano、David Morales-Morales

  DOI：10.1016/s0022-328x(03)00538-2

  日期：2003.8

  The complexes cis-[M(Ph2PC6H4-2-S)2] M=Ni, Pd, Pt were stereoselectively synthesized by transmetallation reactions of [M(Cl)2(NCC6H5)2] M=Pd, Pt or NiCl2·6H2O with [Sn(R)2(Ph2PC6H4-2-S)2] R=Ph, nBu or tBu. The conformation of the Pd and Pt derivatives being unequivocally confirmed by single crystal X-ray diffraction studies showing both metal centers to be into a slightly distorted square planar environment

  配合物的顺式- [M（PH 2 PC 6 H ^ 4 -2-S）2 ] M =镍，钯，铂被立体选择性地通过的金属转移反应合成[M（Cl）的2（NCC 6 ħ 5）2 ] M =具有[Sn（R）2（Ph 2 PC 6 H 4 -2-S）2 ]的Pd，Pt或NiCl 2 ·6H 2 O R = Ph，n Bu或t卜 通过单晶X射线衍射研究明确证实了Pd和Pt衍生物的构型，结果表明两个金属中心都处在稍微扭曲的方形平面环境中，主要变形是由于磷化氢中的芳环引起的空间位阻部分。
• Reaction of a heterotopic P,SAs ligand with group 10 metal(ii) complexes: As–S bond cleavage and the formation of two unusual trinuclear structural isomers for Pd and Pt
  作者：Imola Sárosi、Alexandra Hildebrand、Peter Lönnecke、Luminiţa Silaghi-Dumitrescu、Evamarie Hey-Hawkins

  DOI：10.1039/c2dt12506d

  日期：——

  The synthesis of the heterotopic P,SAs ligand, 1-Ph2AsSC6H4-2-PPh2 (1) and its reaction with [PdCl2(cod)], [PtI2(cod)] (cod = 1,5-cyclooctadiene) and NiCl2·6H2O is reported. Cleavage of the As–S bond of 1 and coordination of the resulting phosphanylthiolato ligand (SC6H4-2-PPh2)− (SC6H4-2-PPh2 = P,S) was observed with formation of [M(P,S)2] (M = Ni, Pd, Pt). In the case of Pd and Pt, not only the mononuclear complexes [M(P,S)2] formed, but also the trimers of [MX(P,S)] ([MX(μ-S-SC6H4-2-PPh2)-κ2S,P}]3 [M = Pd, X = Cl (2) and M = Pt, X = I (4)]). Formation of 2 and 4 was preceded by the trinuclear isomeric intermediates [(cis-M(μ-S-SC6H4-2-PPh2)-κ2S,P}2)-MX2-MX(μ-S-SC6H4-2-PPh2)-κ2S,P}] [M = Pd, X = Cl (3) and M = Pt, X = I (5)]. The crystal structures of 1–5 and a possible reaction mechanism that leads to 2 and 4 are presented.

  报告了异位 P,SAs 配体 1-Ph2AsSC6H4-2-PPh2 (1) 的合成及其与 [PdCl2(cod)]、[PtI2(cod)]（cod = 1,5-环辛二烯）和 NiCl2Â-6H2O 的反应。观察到 1 的 AsâS 键断裂，由此产生的膦酰硫配体 (SC6H4-2-PPh2)â （SC6H4-2-PPh2 = P,S）配位，形成 [M(P,S)2] （M = Ni、Pd、Pt）。在钯和铂的情况下，不仅形成了单核配合物[M(P,S)2]，还形成了[MX(P,S)]的三聚体（[MX(δ-SC6H4-2-Ph2)-δ2S,P}]3 [M = 钯，X = Cl (2) 和 M = 铂，X = I (4)]）。在形成 2 和 4 之前，先出现了三核异构中间体[(cis-M(δ-SC6H4-2-Ph2)-δ2S,P}2)-MX2-MX(δ-SC6H4-2-Ph2)-δ2S,P}][M = Pd, X = Cl (3) 和 M = Pt, X = I (5)]。本文介绍了 1â5 的晶体结构以及生成 2 和 4 的可能反应机理。
• Insertion of Alkynes into Ni−H Bonds:  Synthesis of Novel Vinyl Nickel(II) and Dinuclear Vinyl Nickel(II) Complexes Containing a [P, S]-Ligand
  作者：Lei She、Xiaoyan Li、Hongjian Sun、Jun Ding、Markus Frey、Hans-Friedrich Klein

  DOI：10.1021/om0606340

  日期：2007.1.1

  Reactions of alkynes with nickel hydride complexes bearing a [P, S]-ligand and supported by trimethylphosphine were investigated. Tetracoordinate vinyl nickel(II) complexes 3, 5, and 6 with square-planar geometry were obtained by reacting phenylacetylene, trimethylsilylacetylene, and 1-hexyne with the hydrido nickel complex 1. Reaction of 1,4-bis(trimethylsilylethynyl)benzene with complex 1 proceeds

  研究了炔烃与带有[P，S]-配体并由三甲基膦负载的氢化镍配合物的反应。四配乙烯基镍（II）配合物3，5，和6具有方形平面的几何形状是由苯乙炔，三甲基硅烷基，和1-己炔与氢基镍配合物反应而得到的1。1,4-双（三甲基甲硅烷基乙炔基）苯与配合物1的反应作为单插入进行并得到配合物7，而1,4-双（乙炔基乙苯）苯与1的反应生成双核乙烯基镍（II）配合物8。
• Lightinduced sulfur-dealkylation of phosphino-thioether nickel(0) complexes
  作者：Jang Sub Kim、Joseph H. Reibenspies、Marcetta Y. Darensbourg

  DOI：10.1016/s0020-1693(96)05237-1

  日期：1996.9

  redox events assigned to Ni 11 1 and Ni 1 0 . The one-electron reduction product produced by stoichiometric amounts of Cp2Co can be characterized by EPR. At 100 K rhombic signals show hyperfine coupling to two phosphorus atoms. Complete bulk chemical reduction of complexes 1, 2, 3 and 4 with Na/Hg amalgam provided the corresponding nickel(0) complexes 1R, 2R, 3R and 4R which were isolated as red solutions

  摘要在光化学条件下观察到（Ph2P（o-C6H4）S ）2Ni0中SCH3键的裂解，促使进一步研究镍（0）配合物及其稳定性。四齿P2S'2供体配体（S'=硫醚型S供体），其芳香环并入P至S链中，Ph2P（o- ）S（CH2）3S（o- ）PPh2（arom-PSSP），或S对S链Ph2P（ ）2S （o- ） S（ ）2PPh2（PS-xy-SP）已用于形成四坐标方形方形镍（II）络合物，[（arom- PSSP）Ni]（BF4）2（2）和[（PS-xy-SP）Ni]（ ）2（3）。双齿和四齿配体Ph2P（o- ）S （arom-PSEt）和Ph2P（ ）2S（ ）3S（ ）2PPh2（PSSP）得到类似的络合物[[（arom-PSEt）2Ni]（ ）2（1）和[（PSSP）Ni]（ ）2（4）。 CN中
• Complexes of Ni(II) with sterically-hindered thiolate ligands. Crystal structures of complexes with the [NiS2N2], [NiS2P2] and [NiS2O2] cores
  作者：Eric Block、Gabriel Ofori-Okai、Hyunkyu Kang、Jon Zubieta

  DOI：10.1016/s0020-1693(00)80910-x

  日期：1991.10

  The reactions of NiCl2.6H2O with the thiolate ligands HSC5H3N-3-SiMe3, HSC6H4-2-PPh2 and HSC6H3-6-SiMe3-2-OPPh2 yield the planar mononuclear species [Ni(SC5H3N-3-SiMe3)2], [Ni(SC6H4-2-PPh2)2] and [Ni(SC6H3-6-SiMe3-2-OPPh2)2], respectively. The complexes are electrochemically active, displaying Ni(II)/Ni(III) oxidation processes in the high potential range common to most synthetic Ni(II) complexes. Crystal data: C16H24N2Si2S2Ni: monoclinic P2(1)/n, a = 6.697(1), b = 10.932(2), c = 14.108(3) angstrom, beta = 95.31(1)-degrees, V = 1028.9(8) angstrom-3, Z = 2, D = 1.366 g cm-3. C36H28P2S2Ni: triclinic P1, a = 9.349(3), b = 10.673(3), c = 9.259(2) angstrom, alpha = 105.35(1), beta = 118.52(1), gamma = 91.86(1)-degrees, V = 799.0(9) angstrom-3, Z = 1, D = 1.393 g cm-3. C42H44O2Si2P2S2Ni: monoclinic P2(1)n, a = 12.015(2), b = 27.458(5), c = 12.959(3) angstrom, beta = 96.37(1)-degrees, V = 4248.9(12) angstrom-3, Z = 4, D = 1.285 g cm-3.