Ph2P(CH2)3P(S)Ph2 | 178820-90-1

• 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(CH2)3P(S)Ph2
• 英文别名: [3-(Diphenylphosphanyl)propyl](diphenyl)sulfanylidene-lambda~5~-phosphane；3-diphenylphosphanylpropyl-diphenyl-sulfanylidene-λ5-phosphane
• CAS: 178820-90-1
• 化学式: C₂₇H₂₆P₂S
• 分子量: 444.517
• InChiKey: PNZLXSKKYIZZPP-UHFFFAOYSA-N

物化性质

• 沸点：
  572.6±52.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  32.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  cis-[ruthenium(II)(CO)2Cl2-η1(P)-(Ph2P(CH2)3P(S)Ph2)] 、 Ph2P(CH2)3P(S)Ph2 以 二氯甲烷 为溶剂， 以97%的产率得到cis-[ruthenium(II)(CO)2Cl2-η1(P)-(Ph2P(CH2)3P(S)Ph2)2]
  参考文献：
  名称：

  Carbonyl complexes of ruthenium(II) with unsymmetrical phosphine–phosphinesulfide ligands of the type Ph2P(CH2)nP(S)Ph2, n=1–4

  摘要：

  Reaction of [Ru(CO)(2)Cl-2](n) with ligands Ph2P(CH2)(n) P(S)Ph-2 (n = 1(a), 2(b), 3(c), 4(d)) in 1:1 molar ratio produces complex cis-[Ru(CO)(2)Cl-2(P boolean AND S)](1a) (P boolean AND S = eta(2)-(P, S) Coordinated) and cis -[Ru(CO)(2)Cl-2(P-S)](1b-d) (P-S = eta(1)-(P) coordinated), while 1:2 molar ratio yields complex of the type cis -[Ru(CO)(2)Cl-2(P-S)(2)](2a-d). The complex 2a undergoes partial decarbonylation reaction in CH2Cl2-hexane solution to give a new chelated complex [Ru(CO)Cl(P boolean AND S)(2)]Cl(2a'). Abstraction of halide with AglO(4) from the non-chelated complexes 1b-d and 2a-d afford corresponding chelated complexes [Ru(CO)(2)Cl(P boolean AND S)](ClO4)(3b-d) and [Ru(CO)(2)(P boolean AND S)(2)](ClO4)(2)(4a-d). The molecular structure of the complex 2a' has been determined by single crystal X-ray diffraction. The ruthenium atom is at the Centre of slightly distorted octahedral structure having the two phosphorus atoms of the two chelated P, S coordinated ligands at trans to each other, one CO group and Cl atom completing the coordination sphere. Other complexes have been characterized by elemental analysis, IR, 1H and 31p JHJ NMR spectroscopy. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0277-5387(03)00371-1
• 作为产物：
  描述：

  diphenylphosphane sulfide 生成 Ph2P(CH2)3P(S)Ph2
  参考文献：
  名称：

  Aladzheva, Inga M.; Bykhovskaya, Olga V.; Lobanov, Dmitrii I., Phosphorus, Sulfur and Silicon and the Related Elements, 1996, vol. 111, p. 116

  摘要：

  DOI：

文献信息

• (Diphosphane monosulfide)platinum( <scp>II</scp> ) Complexes for Hydroformylation Reactions: Their Catalytic Activity and a High‐Pressure NMR Mechanistic Study
  作者：Antonio Lofù、Piero Mastrorilli、Cosimo F. Nobile、Gian P. Suranna、Piero Frediani、Jonathan Iggo

  DOI：10.1002/ejic.200501016

  日期：2006.6

  neutral complexes of formula [κ2P,S-(dppmS)Pt(CH3)(Cl)] (1), [κ2P,S-(dppeS)Pt(CH3)(Cl)] (2) and [κ2P,S-(dpppS)Pt(CH3)(Cl)] (3) [dppmS = Ph2PCH2P(S)Ph2; dppeS = Ph2P(CH2)2P(S)Ph2; dpppS = Ph2P(CH2)3P(S)Ph2] are active catalyst precursors for the hydroformylation of 1-octene in methyl isobutyl ketone. The order of reactivity found is3 > 2 > 1. Surprisingly, the cationic complexes [κ2P,S-(dppeS)Pt(CH3)(CH3CN)]BF4

  式 [κ2P,S-(dppmS)Pt(CH3)(Cl)] (1)、[κ2P,S-(dppeS)Pt(CH3)(Cl)] (2) 和 [κ2P,S- (dpppS)Pt(CH3)(Cl)] (3) [dppmS = Ph2PCH2P(S)Ph2; dppeS = Ph2P(CH2)2P(S)Ph2；dpppS = Ph2P(CH2)3P(S)Ph2] 是 1-辛烯在甲基异丁基酮中加氢甲酰化的活性催化剂前体。发现的反应性顺序是 3 > 2 > 1。令人惊讶的是，阳离子复合物 [κ2P,S-(dppeS)Pt(CH3)(CH3CN)]BF4 (4a) 和 [κP,μ-κS-(dppeS)Pt( CH3)}2][BF4]2 (5) 的活性低于类似的中性配合物 2。 高压 NMR 研究表明，在 20 °C、1 至 50 bar 的合成气和 SnCl2 的存在下， 2 和 4a 立即反应形成相同的乙酰复合物
• Regioselectivity and memory effects in palladium catalyzed allylic alkylations with bidentate P^PS donor ligands
  作者：Suzanna C. Milheiro、J.W. Faller

  DOI：10.1016/j.jorganchem.2010.10.022

  日期：2011.2

  bidentate bisphosphine monosulfide ligands, were found to catalyze allylic alkylation reactions with high branched:linear selectivity with some ligands. Some of these catalysts also display a regiochemical memory effect, in which the hemilability and rigidity of the P^PS ligands affect the reaction rate and the degree to which a memory effect is observed.

  一系列配合物，[将Pd（η 3 -C 3 H ^ 5）（P ^ P小号）] [的SbF 6 ]，其中P ^ P小号是二齿膦配位体一硫化物，发现催化具有高支化烯丙基烷基化反应：有一些配体的线性选择性。这些催化剂也显示区域化学记忆效应，其中，所述的hemilability和刚性P ^ P小号配体影响反应速率和被观察到的记忆效应的程度。
• A new series of iodocarbonyl ruthenium (II) complexes with unsymmetrical phosphine–phosphine sulfide ligands of the type Ph2P(CH2)nP(S)Ph2, n=1–4: Isolation and structural investigation
  作者：Dipak Kumar Dutta、Pratap Chutia、J. Derek Woollins、Alexandra M.Z. Slawin

  DOI：10.1016/j.ica.2005.06.051

  日期：2006.2

  Hexa-coordinated chelate complex cis-[Ru(CO)(2)I-2(P boolean AND S)] (1a) (P boolean AND S = eta(2)-(P, S)-coordinated) and penta-coordinated non-chelate complexes cis-(Ru(CO)(2)I-2(P similar to S)] (1b-d) P similar to S = eta(1)-(P)-coordinated are produced by the reaction of polymeric [Ru(CO)(2)I-2](n), with equimolar quantity of the ligands Ph2P(CH2)(n)P(S)Ph-2 n = 1(a), 2(b), 3(c), 4(d)} in dichloromethane at room temperature. The bidentate nature of the ligand a in the complex la leads to the formation of five-membered chelate ring which confers extra stability to the complex. On the other hand, 1:2 (Ru:L) molar ratio reaction affords the hexa-coordinated non-chelate complexes cis,cis,trans[Ru(CO)(2)I-2(P similar to S)(2)](2a-d) irrespective of the ligands. All the complexes show two equally intense terminal v(CO) bands in the range 2028-2103 cm(-1). The v(PS) band of complex la occurs 23 cm-1 lower region compared to the corresponding free ligand suggesting chelation via metal-sulfur bond formation. X-ray crystallography reveals that the Ru(II) atom occupies the center of a slightly distorted octahedral geometry. The complexes have also been characterized by elemental analysis, H-1, C-13 and P-31 NMR spectroscopy. (c) 2005 Elsevier B.V. All rights reserved.
• Complexation of [ω-diphenylphosphinoalkyl]diphenylphosphine sulphides with AgNO3
  作者：Eugenii I. Matrosov、Zoya A. Starikova、Aleksandr I. Yanovsky、Dmitrii I. Lobanov、Inga M. Aladzheva、Olga V. Bykhovskaya、Yuri T. Struchkov、Tatyana A. Mastryukova、Martin I. Kabachnik

  DOI：10.1016/s0022-328x(96)06956-2

  日期：1997.5

  By reaction of [omega-diphenylphosphinoalkyl]diphenylphosphine sulphides Ph2P(CH2)(n)P(S)Ph-2 (n = 2-4) (L-1-L-3) with AgNO3 in CH3CN crystalline complexes with the composition metal:ligand 1:1 [Ag(L-1)NO3, Ag(L-2)NO3, Ap(L-3)NO3] and 1:2 [Ag(L-1)(2)NO3: Ag(L-3)(2)NO3] were isolated. According to the X-ray analysis data. the crystals of Ag(L-1)NO3 are constructed from centrosymmetric dimeric molecules based on the 12-membered macrocycle AgSPCH2CH2PAgSPCH2CH2P. Each of the neutral ligands L-1 is a bridge between two silver ions and each of the silver ions is coordinated by a chelating NO3 group. According to the IR spectra, the other 1:1 groups of the 1:1 complexes are replaced by the complexes also have an analogous structure. In the 1:2 complexes the coordinated NO3 phosphine sulphide ligand. The downfield shifts of the signals of P-III and P-V atoms in P-31 NMR spectra of 1:2 complexes in comparison with the free ligands L-1 and L-3 reflect a participation of the P-III atom and P=S group in complex formation. (C) 1997 Elsevier Science S.A.
• Carbonyl complexes of ruthenium(II) with unsymmetrical phosphine–phosphinesulfide ligands of the type Ph2P(CH2)nP(S)Ph2, n=1–4
  作者：Pratap Chutia、Manab Sharma、Pankaj Das、Nandini Kumari、John Derek Woollins、Alexandra M.Z Slawin、Dipak Kumar Dutta

  DOI：10.1016/s0277-5387(03)00371-1

  日期：2003.8

  Reaction of [Ru(CO)(2)Cl-2](n) with ligands Ph2P(CH2)(n) P(S)Ph-2 (n = 1(a), 2(b), 3(c), 4(d)) in 1:1 molar ratio produces complex cis-[Ru(CO)(2)Cl-2(P boolean AND S)](1a) (P boolean AND S = eta(2)-(P, S) Coordinated) and cis -[Ru(CO)(2)Cl-2(P-S)](1b-d) (P-S = eta(1)-(P) coordinated), while 1:2 molar ratio yields complex of the type cis -[Ru(CO)(2)Cl-2(P-S)(2)](2a-d). The complex 2a undergoes partial decarbonylation reaction in CH2Cl2-hexane solution to give a new chelated complex [Ru(CO)Cl(P boolean AND S)(2)]Cl(2a'). Abstraction of halide with AglO(4) from the non-chelated complexes 1b-d and 2a-d afford corresponding chelated complexes [Ru(CO)(2)Cl(P boolean AND S)](ClO4)(3b-d) and [Ru(CO)(2)(P boolean AND S)(2)](ClO4)(2)(4a-d). The molecular structure of the complex 2a' has been determined by single crystal X-ray diffraction. The ruthenium atom is at the Centre of slightly distorted octahedral structure having the two phosphorus atoms of the two chelated P, S coordinated ligands at trans to each other, one CO group and Cl atom completing the coordination sphere. Other complexes have been characterized by elemental analysis, IR, 1H and 31p JHJ NMR spectroscopy. (C) 2003 Elsevier Ltd. All rights reserved.