trans-bis((2-thiolatoethyl)diphenylphosphine)nickel(II) | 90668-33-0

• 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: trans-bis((2-thiolatoethyl)diphenylphosphine)nickel(II)
• 英文别名: 2-diphenylphosphanylethanethiolate;nickel(2+)
• CAS: 90668-33-0
• 化学式: C₂₈H₂₈NiP₂S₂
• 分子量: 549.3
• InChiKey: LHSOAHAHOHFEBF-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  5.33
• 重原子数：
  33
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-bis((2-thiolatoethyl)diphenylphosphine)nickel(II) 在 Et₃OBF₄ 、 pyridine 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 生成 bis((μ-S-(2-thiolatoethyl)-diphenylphosphine))((2-thiolatoethyl)diphenyl-phosphine)dinickel(+1)
  参考文献：
  名称：

  一种新型的不对称硫代酸酯桥联配合物双[μ - S-（2-噻吩乙基）-二苯基膦] [（2-硫代乙基）二苯基-膦] dinickel（+1）离子的制备和性质

  摘要：

  标题阳离子（=倪2 L）形成为各种反应（的方案1和2中含有Ni系统）2+和（2- thiolatoethyl） -二苯基膦（= L - ）在不存在配位阴离子中的镍2 + / L -比率>在非极性或中等极性介质0.5。分离出固体[Ni 2 L 3 ] CIO 4和[Ni 2 L 3 ] BPh 4。Job的图证实了溶液中的Ni 2 L-化学计量。31 P-NMR数据与≥97％Ni 2一致L（相对于假设的Ni 3 L的⩽3％）处于平衡状态，并支持建议的构型（图2）。NIL之间的平衡2 + NIL 2溴2和Ni 2 L +溴-与CH溶剂组成变化23氯2 / EtOH中的混合物。形成的Ni的速率2大号2溴2选自Ni 2在CH L和溴化物（过量高）2氯2是一阶在[倪2 L] TOT而是取决于比[卜4NBr] tot / [Ni 2 L 3 ·ClO 4 ] tot，即使溴化物过量过多也是如此。这可以通过在作为Ni

  DOI：

  10.1002/hlca.19840670304
• 作为产物：
  描述：

  以 neat (no solvent, solid phase) 为溶剂， 生成 trans-bis((2-thiolatoethyl)diphenylphosphine)nickel(II)
  参考文献：
  名称：

  Darensbourg, Marcetta Y.; Tuntulani, Thawatchai; Reibenspies, Joseph H., Inorganic Chemistry, 1994, vol. 33, # 3, p. 611 - 613

  摘要：

  DOI：
• 作为试剂：
  描述：

  二氧化硫 、 氧气 在 trans-bis((2-thiolatoethyl)diphenylphosphine)nickel(II) NaSPh 作用下， 以 甲醇 为溶剂， 生成 硫酸酯
  参考文献：
  名称：

  Structure/Function Relationships in Ligand-Based SO2/O2 Conversion to Sulfate As Promoted by Nickel and Palladium Thiolates

  摘要：

  The dithiolate complex [1,5-bis(mercaptoethyl)-1,5-diazacyclooctane]Pd(II), (bme-daco)Pd-II or Pd-1, whose structure was determined by X-ray crystallography (monoclinic P2(1)/m space group with a = 6.1680(10) Angstrom, b = 15.715(5) Angstrom, c = 6.5930(10) Angstrom, beta = 107.090(10)degrees, Z = 2, R = 0.0291, R(W) = 0.0718), has been added to a group of metal thiolates which form sulfur-site SO2 adducts. Exposure of the Pd-l complex to SO2 in methanol results in the precipitation of yellow/orange crystalline Pd-1 SO2: monoclinic space group, P2(1)/c (No. 14), with a 8.928(2) Angstrom, b = 14.655(4) Angstrom, c = 11.067(2) Angstrom, beta = 97.29(2)degrees, Z = 4, R = 0.0348, R(W) = 0.0944. Analogous thiolate-SO2 adducts based on (bme-daco)Ni-II, Ni-1 . SO2, (Ph(2)PCH(2)CH(2)S)(2)Ni-II, Ni-2 . SO2, and (bme*-daco)Ni-II, Ni-1*. SO2, also precipitate from methanol. To explore the transformation of SO2 to SO42- in these adducts, the following three factors expected to control the sulfate-forming reaction have been examined: (i) the stability of SO2 adducts; (ii) the oxidizability of the metal thiolate or its tendency to generate disulfide products on oxidation; and (iii) the ability of the metal thiolates to react with O-2 and produce sulfur-oxygenated products. The studies indicate that the last factor is the most important influence on SO2 oxygenation. A possible mechanism involves the transient formation of an SO2-stabilized sulfperoxide intermediate, which behaves as a nucleophile and further reacts with SO2 to produce SO42-. The use of the aforementioned metal thiolate complexes as catalysts for SO2 oxygenation in the presence of a sacrificial electron donor has also been explored; simple salts such as NiCl2 and NiSO4 are more efficient than the complexes.

  DOI：

  10.1021/ic00129a013

文献信息

• 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）SCH3）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-C6H4）S（CH2）3S（o-C6H4）PPh2（arom-PSSP），或S对S链Ph2P（CH2）2SCH2（o-C6H4）CH2S（CH2）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]（BF4）2（3）。双齿和四齿配体Ph2P（o-C6H4）SCH2CH3（arom-PSEt）和Ph2P（CH2）2S（CH2）3S（CH2）2PPh2（PSSP）得到类似的络合物[[（arom-PSEt）2Ni]（BF4 ）2（1）和[（PSSP）Ni]（BF4）2（4）。CH3CN中
• Chojnacki, Stephen S.; Hsiao, Yui-May; Darensbourg, Marcetta Y., Inorganic Chemistry, 1993, vol. 32, # 16, p. 3573 - 3576
  作者：Chojnacki, Stephen S.、Hsiao, Yui-May、Darensbourg, Marcetta Y.、Reibenspies, Joseph H.

  DOI：——

  日期：——
• Organometallic chemistry of sulfur/phosphorus donor ligand complexes of nickel(II) and nickel(0)
  作者：Yui May Hsiao、Stephen S. Chojnacki、Pamela Hinton、Joseph H. Reibenspies、Marcetta Y. Darensbourg

  DOI：10.1021/om00027a041

  日期：1993.3

  The X-ray crystal structures and electrochemical properties as well as chemical reactivity o the thioether complexes [Ni(Ph2PCH2CH2SEt)2][BF4]2 (5) and [Ni(Ph2PCH2CH2SCH2CH2CH2SCH2CH2PPh2)][BF4]2 (6), [Ni(PSSP)]2+, are compared with the thiolate Ni(Ph2PCH2CH2S)2 (4). Complex 4 crystallized in the orthorhombic space group Pbca (No. 61) with a 9.204(2) angstrom, b = 15.766(3) angstrom, c = 17.177(3) angstrom, V = 2492.6(8) angstrom3 Z = 4, and fin R = 0.050 (R, = 0.050) for 2212 unique reflections. Complex 5 crystallized in the monoclinic space group P2(1)/c, with a = 10.267(2) angstrom, b = 13.102(2) angstrom, c = 13.263(2) angstrom, beta = 93.750(10)-degrees, V = 1780.3(5) angstrom3, Z = 2, and final R = 0.076 (R(w) = 0.072) for 1777 unique reflections. The square-planar structures of 4 and 5 have sulfur donors in a trans arrangement and show a 0.04-angstrom lengthening of both the Ni-S and Ni-P bonds on going from the thiolate to the thioether complex. Within the CH3CN solvent window, the cyclic voltammograms of 5 and 6 show two reversible redox events assigned to Ni(II/I) and Ni(I/0), whereas the thiolate 4 shows only a sulfur-based irreversible oxidation and no reduction. Complexes 5 and 6 can be chemically reduced to Ni0 species, 5R and 6R, with Na/Hg amalgam. The H-1 NMR spectra of the reduced complexes indicate loss of one thioether donor for 5R and both for 6 . Protonation of the reduced species produced a Ni-H and reaction with both CH3I or CH3C(=O)Cl gave rise to Ni-CH3 and NiC(O)CH3 functionalities, respectively. The tetradentate derivatives [HNi(PSSP)]+ and [CH3Ni(PSSP)]+ are more stable than their bidentate analogues and show loss of reversible redox activity; i.e., the cyclic voltammograms find no evidence for stable Ni(I)-H or Ni(I)-CH3, or for Ni(III)-H or Ni(III)-CH3 species. The NiC(O)CH3 compounds rapidly and reversibly decarbonylate in solution (at temperatures >-30-degrees-C). A contrast of the abilities of structurally analogous P-SR vs N-SR ligands to stabilize subvalent nickel and organonickel functionalities is made.
• Structure/Function Relationships in Ligand-Based SO2/O2 Conversion to Sulfate As Promoted by Nickel and Palladium Thiolates
  作者：Marcetta Y. Darensbourg、Thawatchai Tuntulani、Joseph H. Reibenspies

  DOI：10.1021/ic00129a013

  日期：1995.12

  The dithiolate complex [1,5-bis(mercaptoethyl)-1,5-diazacyclooctane]Pd(II), (bme-daco)Pd-II or Pd-1, whose structure was determined by X-ray crystallography (monoclinic P2(1)/m space group with a = 6.1680(10) Angstrom, b = 15.715(5) Angstrom, c = 6.5930(10) Angstrom, beta = 107.090(10)degrees, Z = 2, R = 0.0291, R(W) = 0.0718), has been added to a group of metal thiolates which form sulfur-site SO2 adducts. Exposure of the Pd-l complex to SO2 in methanol results in the precipitation of yellow/orange crystalline Pd-1 SO2: monoclinic space group, P2(1)/c (No. 14), with a 8.928(2) Angstrom, b = 14.655(4) Angstrom, c = 11.067(2) Angstrom, beta = 97.29(2)degrees, Z = 4, R = 0.0348, R(W) = 0.0944. Analogous thiolate-SO2 adducts based on (bme-daco)Ni-II, Ni-1 . SO2, (Ph(2)PCH(2)CH(2)S)(2)Ni-II, Ni-2 . SO2, and (bme*-daco)Ni-II, Ni-1*. SO2, also precipitate from methanol. To explore the transformation of SO2 to SO42- in these adducts, the following three factors expected to control the sulfate-forming reaction have been examined: (i) the stability of SO2 adducts; (ii) the oxidizability of the metal thiolate or its tendency to generate disulfide products on oxidation; and (iii) the ability of the metal thiolates to react with O-2 and produce sulfur-oxygenated products. The studies indicate that the last factor is the most important influence on SO2 oxygenation. A possible mechanism involves the transient formation of an SO2-stabilized sulfperoxide intermediate, which behaves as a nucleophile and further reacts with SO2 to produce SO42-. The use of the aforementioned metal thiolate complexes as catalysts for SO2 oxygenation in the presence of a sacrificial electron donor has also been explored; simple salts such as NiCl2 and NiSO4 are more efficient than the complexes.
• Darensbourg, Marcetta Y.; Tuntulani, Thawatchai; Reibenspies, Joseph H., Inorganic Chemistry, 1994, vol. 33, # 3, p. 611 - 613
  作者：Darensbourg, Marcetta Y.、Tuntulani, Thawatchai、Reibenspies, Joseph H.

  DOI：——

  日期：——