1,3-bis(diphenylphosphino)buta-1,3-diyne | 7652-17-7

• 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: 1,3-bis(diphenylphosphino)buta-1,3-diyne
• 英文别名: 1,4-Bis(diphenylphosphino)buta-1,3-diyne；1,4-bis(diphenylphosphanyl)butadiyne；1,4-bis(diphenylphosphino)butadiyne；bis(diphenylphosphino)butadiyne；PPh2C2C2Ph2；Phosphine, 1,3-butadiyne-1,4-diylbis[diphenyl-；4-diphenylphosphanylbuta-1,3-diynyl(diphenyl)phosphane
• CAS: 7652-17-7
• 化学式: C₂₈H₂₀P₂
• 分子量: 418.414
• InChiKey: JSPPXLVWOGVRFS-UHFFFAOYSA-N

物化性质

• 熔点：
  105 °C
• 沸点：
  556.6±33.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  30
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1,3-bis(diphenylphosphino)buta-1,3-diyne 在 双氧水 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以98%的产率得到1,4-bis(diphenylphosphinoyl)buta-1,3-diyne
  参考文献：
  名称：

  铑催化的1，4-双（二苯基膦酰基）buta-1,3-diyne与束缚二炔的双[2 + 2 + 2]环加成反应：NU-BIPHEP双芳基二膦酸酯的模块化，高度通用的单罐合成。

  摘要：

  铑催化的1,4-双（二苯基膦酰基）丁1,3-二炔与束缚二炔的双[2 + 2 + 2]环加成反应为合成新型对位联芳基二膦提供了一种简单的单釜法，NU-BIPHEP。这种方法代表了对现有多步骤程序的重大改进。这些二膦的对映纯路易斯酸铂络合物是羰基-烯和Diels-Alder反应的高效催化剂，钌二膦二胺络合物催化酮的不对称还原，得到的ee可以与用BINAP对应的ee竞争。

  DOI：

  10.1021/ol702390p
• 作为产物：
  描述：

  丁二炔 、 二苯基氯化膦 在 正丁基锂 作用下， 生成 1,3-bis(diphenylphosphino)buta-1,3-diyne
  参考文献：
  名称：

  Some transition metal complexes of the diacetylenic diphosphine Ph2PC2C2PPh2: synthesis and crystal structures

  摘要：

  Several complexes of the acetylenic ditertiary phosphine, Ph2PC2C2PPh2, containing Mo, W, Fe, Ru or Au have been prepared; one C = C triple bond in the Mo, W or Fe derivatives has been co-ordinated to Co2(CO)6 or Pt(PPh3)2 groups. Crystal structure determinations of [{Fe(CO)4}2(mu-PPh2C2C2PPh2)] 3 and [Co2{mu-eta-2-[(OC)5W(PPh2)]C = C[C2(PPh2)W(CO)5]}(CO)6] 7 show that the P-bonded M(CO)n groups take up transoid positions; in 3, the PCCCCP chain, which is situated about a centre of inversion, is nearly linear [P-C-C, 173.2(5); C-C-C 179.7(6) for molecule a and 174.7(5) and 177.6(6)-degrees, respectively, for molecule b] with C = C distances of 1.192(7) angstrom [1.201(6) angstrom, molecule b]. in 7, co-ordination of the Co2(CO)6 group to one C = C bond lengthens that bond by 0.13 angstrom, compared with the unco-ordinated C = C bond, and induces bend-back of the substituents of 141-143(1)-degrees (PPh2) and 145-146(1)-degrees (C2PPh2) Crystals of 3 are triclinic, space group P1BAR, a = 11.261(1), b = 12.456(2), c = 13.061(2) angstrom, alpha = 79.23(2), beta = 75.73(1), gamma = 78.75(2)-degrees, Z = 2; 2870 data were refined to R = 0.042, R' = 0.046. Crystals of 7 are triclinic, space group P1BAR, a = 17.940(4), b = 19.695(4), c = 16449(2) angstrom, alpha = 111.92(1), beta = 108.83(1), gamma = 100.29(2)-degrees, Z = 4; 5942 data were refined to R = 0.055, R = 0.056.

  DOI：

  10.1039/dt9920001157

文献信息

• [EN] BIARYL DIPHOSPHINES<br/>[FR] BIARYLDIPHOSPHINES
  申请人：UNIV NEWCASTLE

  公开号：WO2009044130A1

  公开（公告）日：2009-04-09

  A compound of formula (I):wherein: X is selected from O, S, NRN1, PRP1, SiRSi1RSi2, BRB1, CRC1RC2 and (CRC1RC2)2,, where RN1 is selected from H, C1-7 alkyl sulfonyl, benzyl and C1-7 alkyl, RP1 is selected from C1-7 alkyl and C5-7 aryl, RSi1 and RSi2 are independently selected from H, C1-7 alkyl, benzyl and C5-7 aryl, RB1 is selected from C1-7 alkyl, C5-7 aryl, C1-7 alkyloxy, C5-7 aryloxy, and RC1 and RC2 are independently selected from H, C1-7 alkyl, and C1-7 alkylester; if X is (CRC1RC2)2 then, the two carbon atoms may form part of a fused carbocyclic or heterocyclic ring, having between 3 and 7 ring atoms; R1 is selected from H, hydroxy, C1-7 alkyl, C1-7 alkyloxy, silyloxy, C1-7 alkylester; R2 is selected from H, hydroxy, C1-7 alkyl, C1-7 alkyloxy, silyloxy, C1-7 alkylester; and RP is selected from C5-20 aryl, di(C1-7 alkyl) amino, C1-7 alkoxy, chloro and C1-7 alkyl.

  式(I)的化合物：其中：X选自O、S、NRN1、PRP1、SiRSi1RSi2、BRB1、CRC1RC2和(CRC1RC2)2，其中RN1选自H、C1-7烷基磺酰基、苄基和C1-7烷基，RP1选自C1-7烷基和C5-7芳基，RSi1和RSi2分别选自H、C1-7烷基、苄基和C5-7芳基，RB1选自C1-7烷基、C5-7芳基、C1-7烷氧基、C5-7芳氧基，RC1和RC2分别选自H、C1-7烷基和C1-7烷酯基；如果X为(CRC1RC2)2，则两个碳原子可以构成具有3至7个环原子的融合环烷或杂环；R1选自H、羟基、C1-7烷基、C1-7烷氧基、硅烷氧基、C1-7烷酯基；R2选自H、羟基、C1-7烷基、C1-7烷氧基、硅烷氧基、C1-7烷酯基；RP选自C5-20芳基、二(C1-7烷基)氨基、C1-7烷氧基、氯和C1-7烷基。
• Rhodium(I) acetylacetonato complexes containing phosphinoalkynes as catalysts for the hydroboration of vinylarenes
  作者：Christopher M Vogels、Andreas Decken、Stephen A Westcott

  DOI：10.1139/v05-242

  日期：2006.2.1

  Three novel rhodium(I) acetylacetonato (acac) complexes bearing phosphinoalkynes (Ph₂PC≡C-t-Bu, Ph₂PC≡CPPh₂, and Ph₂PC≡CC≡CPPh₂) have been prepared and characterized fully. Addition of B₂cat₃ (cat = 1,2-O₂C₆H₄) to Rh(acac)(Ph₂PC≡C-t-Bu)₂ (1a) led to zwitterionic Rh(η⁶-catBcat)(Ph₂PC≡C-t-Bu)₂ (2a), the first example of this type of compound to contain monodentate phosphine ligands. All new rhodium complexes have been investigated for their ability to catalyse the hydroboration of vinylarenes.Key words: catalysis, hydroboration, phosphinoalkynes, regioselectivity, rhodium.

  我们制备了三种新型乙酰丙酮(acac)铑(I)配合物，并对其进行了全面表征，这些配合物含有膦炔（Ph2PC≡C-t-Bu、Ph2PC≡CPPh2 和 Ph2PC≡CC≡CPPh2）。在 Rh(acac)(Ph2PC≡C-t-Bu)2（1a）中加入 B2cat3（cat = 1,2-O2C6H4）可得到齐聚物 Rh(η6-catBcat)(Ph2PC≡C-t-Bu)2（2a），这是此类化合物中第一个含有单齿膦配体的实例。我们对所有新的铑配合物催化乙烯基炔的氢硼化反应的能力进行了研究。
• Investigation of Electron Delocalization and Ultrafast Studies of Ru^II/Os^II Dyads with Ethynyl/Butadiynyl-Bridged Polyphosphines
  作者：Dengfeng Xu、Jin Z. Zhang、Bo Hong

  DOI：10.1021/jp003907s

  日期：2001.8.1

  (M = RuII, OsII) molecules. Electronic communication through polyphosphine/polyyne spacers is found to decrease upon increase of the carbon chain length, and the comproportionation constant Kc was calculated as 14−18 for species with C2P2 and ca. 4 for the ones with C4P2. In addition, fast intramolecular energy transfer from the RuII-based donor to the OsII-based acceptor, with rate constant of (2.4−2

  对一系列具有 M(bpy)2Cl 基部分的单体、同双金属和异双金属配合物（M = RuII 和 OsII) 以及乙炔基和丁二炔基桥连的多膦，即 Ph2PC⋮CPPh2 (C2P2) 和 Ph2PC⋮CC⋮CPPh2 (C4P2)。这些配合物是通过间隔物与 cis-M(bpy)2Cl2 的反应或通过两个 [Cl(bpy)2M(Ph2PC⋮CH)](PF6) (M = RuII, OsII) 分子之间的偶联反应合成的。发现通过聚膦/聚炔间隔物的电子通信随着碳链长度的增加而减少，对于具有 C2P2 和 ca 的物种，比例常数 Kc 计算为 14-18。4 用于具有 C4P2 的那些。此外，
• Homobimetallic vanadium d1–d1 complexes: structure and magnetism
  作者：Robert Choukroun、Bruno Donnadieu、Isabelle Malfant、Simone Haubrich、Richard Frantz、Christian Guerin、Bernard Henner

  DOI：10.1039/a704461e

  日期：——

  From Me3SiCC–CCSiMe3 and Ph2PCC–CCPPh2 diynes and vanadocene VCp2, homobimetallic vanadium d1–d1 complexes are synthesized and characterized by X-ray crystal structures of (Cp2V)2(1-2η:3-4η-RCC–CCR), (R = SiMe3 1 PPh2 2); magnetic moments of both complexes from 300 to 2 K indicate an antiferromagnetic J exchange coupling of –10.5 and –59.8 cm–1 for 1 and 2, respectively.

  从Me3SiCCâCCSiMe3和Ph2PCCâCCPPh2二炔和二茂钒VCp2合成了同双金属钒d1âd1配合物，并通过X射线晶体结构表征了(Cp2V)2(1-2δ-:3-4δ--RCCâCCR)，(R = SiMe3 1 PPh2 2)；两种配合物在300至2 K的磁矩表明反铁磁J交换耦合为â10.5和â59.8 cmâ1 。
• Tungsten coordination chemistry of 1,4-bisdiphenylphosphinobutadiyne — Synthesis of coordination macrocycles and factors controlling diyne cycloaddition
  作者：Jordan A Tsui、Timothy M Bolton、Brian T Sterenberg

  DOI：10.1139/v08-123

  日期：2009.1.1

  The 1:1 reaction of [W(CO)₄(2-picoline)₂] (1) with Ph₂PCtriple bondC-Ctriple bondCPPh₂ (2) led to [cis-W(CO)₄]₂(µ-Ph₂PC₄PPh₂)₂} (3), in which two bis(diphenylphosphino)butadiyne ligands bridge two tetracarbonyltungsten centres. Reaction of 1 with excess 2 led to [cis-W(CO)₄(Ph₂PC₄PPh₂-κ¹-P)₂] (4), in which two dangling bis-phosphines are coordinated to one metal centre, and reaction of 2 with two equivalents of 1 led to [W(2-picoline)(CO)₄]₂(µ-Ph₂PC₄PPh₂)} (5), in which one ligand bridges two tungsten centres. Combination of 4 and 5 led to the trimeric complex [cis-W(CO)₄]₃(µ-Ph₂PC₄PPh₂)₃} (6), in which three tetracarbonyltungsten centres are bridged by three bisdiphenylphosphinobutadiyne ligands. The dimeric complex 3 showed no reactivity towards alkyne cycloaddition; however, the trimeric complex 6 undergoes cycloaddition at moderate temperatures to form [W(CO)₄]₃[µ₃-C₁₂(Ph₂P)₆]} (8), which contains a cyclododecatrienetriyene ring. Comparison of structural data for the template complexes 3 and 6, as well that of previously described platinum template complexes, suggests that alkyne cycloaddition reactions are favoured by proximity of the alkynyl carbons α to phosphorus in adjacent ligands.Key words: coordination chemistry, diyne, cycloaddition, templated reaction, tungsten.

  W(CO)4(2-picoline)2] (1) 与 Ph2PCtriple bondC-Ctriple bondCPPh2 (2) 发生 1:1 反应，生成[顺式-W(CO)4]2(μ-Ph2PC4PPh2)2} (3)，其中两个双(二苯基膦)丁二炔配体连接两个四碳钨中心。1 与过量的 2 反应生成[顺式-W(CO)4(Ph2PC4PPh2-κ1-P)2](4)，其中两个悬垂双膦配位到一个金属中心；2 与两个当量的 1 反应生成[W(2-吡啶)(CO)4]2(μ-Ph2PC4PPh2)}(5)，其中一个配体桥接两个钨中心。4 和 5 的组合产生了三元复合物[顺式-W(CO)4]3(µ-Ph2PC4PPh2)3}（6），其中三个双二苯基膦丁二炔配体桥接了三个四碳基钨中心。二聚络合物 3 对炔烃环加成没有反应活性；但是，三聚络合物 6 在中等温度下会发生环加成反应，形成[W(CO)4]3[μ3-C12(Ph2P)6]} (8)，其中含有一个环十二碳三乙烯环。比较模板配合物 3 和 6 以及以前描述的铂模板配合物的结构数据表明，炔基碳原子 α 与相邻配体中的磷接近，有利于炔环化反应。