diisopropylphosphine(diphenylphosphine)methane | 62263-67-6

• 物质功能分类: 有机原料 - 烃类化合物及其衍生物
• 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: diisopropylphosphine(diphenylphosphine)methane
• 英文别名: diisopropylphosphino(diphenylphosphino)methane；Ph2PCH2PPrⁱ2；P(i)Pr2CH2PPh2；Phosphine, [[bis(1-methylethyl)phosphino]methyl]diphenyl-；diphenylphosphanylmethyl-di(propan-2-yl)phosphane
• CAS: 62263-67-6
• 化学式: C₁₉H₂₆P₂
• 分子量: 316.363
• InChiKey: YMHXTUSVGZDWGN-UHFFFAOYSA-N

物化性质

• 沸点：
  395.8±25.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.37
• 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：

  diisopropylphosphine(diphenylphosphine)methane 以 乙醚 、 正己烷 为溶剂， 生成 [RhHCl2(κ(2)-Ph2PCH2PiPr2)]
  参考文献：
  名称：

  合成，分子结构，和的反应性：（π烯丙基）氯化铑（I）配合物的体积庞大的双（膦）甲烷R” 2 PCH 2 P我镨2作为配体

  摘要：

  该π烯丙基络合物的[Rh（η 3 -2- RC 3 ħ 4）（κ 2 -R ' 2 PCH 2 P我镨2）]（R = H，甲基; R'=我镨中，Cy中，Ph） （2 - 7）得自制备的RhCl（η 4 -C 8 ħ 12）] 2，2-RC 3 ħ 4 MGX，和R” 2 PCH 2 P我镨2通过的[Rh（η 3 -2- RC 3 ħ 4）（η 4 -C 8H 12）]作为中间体。的反应2 - 4与布朗斯台德（R = H）的酸HX（X =氯，CF 3 CO 2，CF 3 SO 3）导致了烯丙基-金属键的断裂和所述monohydridorhodium的形成（III）的化合物[ RhHX 2（κ 2 -R” 2 PCH 2 P我镨2）]（8 - 12）。NMR的8到12温度可变测量证实了这些化合物在溶液中是有反应的。的反应2 - 4用CO给在初始步骤中的1：1加合物的[Rh（η 3 -C 3 H

  DOI：

  10.1021/om980062m
• 作为产物：
  描述：

  methyldiphenylphosphine borane 在 正丁基锂 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 37.0h， 生成 diisopropylphosphine(diphenylphosphine)methane
  参考文献：
  名称：

  Insights into the Stability and Structures of Phosphine-Boranes and Their α-Metalated Derivatives

  摘要：

  The reaction between iPr(2)PCl and Ph2P(BH3)CH2Li gives the mixed phosphine/phosphine-borane Ph2P(BH3)CH(2)PiPr(2) (1a) in good yield. Thermolysis of 1a leads to borane migration and the formation of Ph(2)PCH2P(BH3)iPr(2) (2a) along with small amounts of Ph2P(BH3)CH2P(BH3)iPr(2) (3a) and Ph2PCH2PiPr2 (4a). Compound 3a may be synthesized directly from the reaction of 1a with BH3.SMe2, while 4a can be prepared cleanly by heating 1a in methanol under reflux. Kinetic studies on the conversion of 1a to 2a reveal the reaction to be apparently first order in 1a, suggesting a dissociative process, and yield the activation parameters H = 63 +/- 8 kJ mol1, S = -145 +/- 24 J K1 mol1, and G = 106 8 kJ mol1, the negative entropy of activation conversely suggesting an associative process. DFT studies suggest that concerted migration of borane within a molecule of 1a is disfavored, but that both the dissociative and associative mechanisms for borane migration operate simultaneously. Metalation of 1a4a with nBuLi in the presence of tmeda gives the complexes [{Ph2P(BH3)}CHPiPr(2)]Li(tmeda) (1b), [Ph2PCH{P(BH3)iPr(2)}]Li(tmeda) (2b), [{Ph2P(BH3)}CH{P(BH3)iP(r)2}]Li(tmeda) (3b), and [Ph(2)PCHPiPr(2)]Li(tmeda) (4b), respectively, which adopt similar structures in the solid state. Analysis of the crystal structures suggests that the phosphine-borane groups stabilize the adjacent charge to a greater extent than the phosphine groups. This is supported by DFT calculations, which show that the greatest delocalization of negative charge from the carbanion is into the PC(Ph) or PC(Pr) sigma-orbitals of the phosphine-borane substituents.

  DOI：

  10.1021/om5005995

文献信息

• A series of mononuclear ruthenium(II) complexes with sterically demanding bis(phosphino)methanes and arsino(phosphino)methanes as ligands
  作者：Helmut Werner、Guido Fries、Birgit Weberndörfer

  DOI：10.1016/s0022-328x(00)00339-9

  日期：2000.8

  Hacac-f6. The preparation of the non-fluorinated bis(acac) compound [Ru(η2-acac)2(κ2-iPr2PCH2PPh2)] (12), which could not be obtained from 2 and Hacac, was achieved by ligand exchange from 10 and acetylacetone in the presence of Na2CO3. The reaction of 10 with CO and CNtBu gave by partial opening of the chelate rings the substitution products [Ru(OC6Cl5)2(CO)(κ2-iPr2PCH2PPh2)] (13) and [Ru(OC6Cl5)2(CNtBu)3(κ1-Ph2PCH2PiPr2)]

  的双（η 3 -2-甲基烯丙基）钌（II）配合物的[Ru（η 3 -2-MEC 3 ħ 4）2（κ 2 -R 2 PCH 2 PPH 2）]（R =我镨2中，Cy 3）从环辛1.5 -二烯衍生物制备的[Ru（η 3 -2-MEC 3 ħ 4）2（η 4 -C 8 ħ 12）]（1）和非对称的双（膦）甲烷- [R 2 PCH 2 PPh 2（R =我Pr，Cy）。的治疗2与苯甲酸和与在存在乙酸我镨2 PCH 2 PPH 2的带动下，allylmetal键的质子辅助裂解，向双形成之后（羧酸根）合钌（II）的化合物4和5a / 5b分别。类似地，双（三氟乙酸盐）的[Ru（η 1 -O 2 CCF 3）2（κ 2 -我镨2 PCH 2 P我镨2）2 ]（7制备），并通过X射线晶体学确定分子结构。反应2和3与六氟丙酮，得到螯合络合物的[Ru（η 2 -acac- ˚F 6）2（κ 2 -R 2 PCH
• Scope and Limitations of the Peterson Olefination Reaction as a Route to Vinylidene Phosphanes
  作者：Keith Izod、William McFarlane、Brent V. Tyson

  DOI：10.1002/ejoc.200300683

  日期：2004.3

  vinylidene phosphanes [nPr2P(BH3)](Me3Si)C=CH2 (6), (Ph2P)(iPr2P)C=CH2 (7), [nPr2P(S)](Me3Si)C=CH2 (10), [Ph2P(S)][iPr2P(S)]C=CH2 (11) and [Ph2P(S)][Me2P(S)]C=CH2 (12) are readily accessible by the Peterson olefination reaction compound 7 is obtained by deprotection of the corresponding borane adduct [Ph2P(BH3)][iPr2P(BH3)]C=CH2 with pyrrolidine}. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany

  彼得森烯化反应已被研究作为获得新型 P 取代烯烃的途径。[(nPr2P)2(Me3Si)C]Li 和多聚甲醛之间的反应干净利落地得到对称的亚乙烯基磷烷 (nPr2P)2C=CH2 (4)，产率非常好。相比之下，[(R2P)(Me3Si)2C]Li（R = Me，nPr）和多聚甲醛之间的反应会产生不包含预期亚乙烯基种类的复杂产物混合物。然而，不对称亚乙烯基膦[nPr2P(BH3)](Me3Si)C= (6), (Ph2P)(iPr2P)C= (7), [nPr2P(S)](Me3Si)C= (10) , [Ph2P(S)][iPr2P(S)]C= (11) 和 [Ph2P(S)][Me2P(S)]C= (12) 很容易通过 Peterson 烯化反应获得 化合物 7 是通过将相应的硼烷加合物 [Ph2P( )][iPr2P( )]C= 与吡咯烷脱保护获得}。(©
• A convenient synthesis of bis(phosphino)methanes: Formation of a nickel(II) bis(phosphino)methane monoxide complex
  作者：Juan Cámpora、Celia M. Maya、Inmaculada Matas、Birgit Claasen、Pilar Palma、Eleuterio Álvarez

  DOI：10.1016/j.ica.2005.12.053

  日期：2006.7

  chlorophosphines ClPR 2 ′ provides ready access to a range of symmetrical or non-symmetrical diphosphinomethanes R 2 PCH 2 PR 2 ′ . The products are obtained cleanly and can be used directly in the synthesis of transition metal complexes. This is illustrated by the preparation and structural characterization of the corresponding NiCl2(P–P) derivatives.

  摘要（三甲基甲硅烷基）甲基膦R2PCH2SiMe3与氯膦ClPR 2'的反应提供了一系列对称或非对称二膦甲烷R 2 PCH 2 PR 2'的容易获得的途径。产物是干净获得的，可以直接用于过渡金属配合物的合成中。相应的NiCl2（P–P）衍生物的制备和结构表征说明了这一点。
• Synthesis and structural characterization of luminescent gold(<scp>i</scp>) derivatives with an unsymmetric diphosphine
  作者：Manuel Bardají、Peter G. Jones、Antonio Laguna、M. Dolores Villacampa、Noelia Villaverde

  DOI：10.1039/b309116c

  日期：——

  mono-bridged digold(I) derivatives with an unsymmetric diphosphine, namely, [(AuX)2(μ-PiPr2CH2PPh2)] (X = Cl, Br, I, C6F5, S2CN(CH2Ph)2) and the mononuclear gold(III) complex [Au(C6F5)3(PiPr2CH2PPh2)]. X-ray diffraction studies show intramolecular gold(I)–gold(I) interactions of 3.4179(2), 3.1660(2) and 3.0926(3) Å, respectively, for X = Cl, Br and C6F5. The pentafluorophenyl derivative emits at 445 nm at

  我们已合成了一系列单声道桥接digold的（我）衍生物与非对称二膦，即，[（AUX）2（μ-P我镨2 CH 2 PPH 2）]（X =氯，溴，I，C 6 F 5，S 2 CN（CH 2 Ph）2）和单核金（III）络合物[Au（C 6 F 5）3（P i Pr 2 CH 2 PPh 2）]。X射线衍射研究表明，对于X = Cl，Br和C 6 F 5，分子内的金（I）-金（I）相互作用分别为3.4179（2），3.1660（2）和3.0926（3）Å 。这五氟苯基衍生物在室温下以445 nm的固态发射。该化合物和卤代衍生物在低温下在440-486 nm范围内发光。我们还制备双桥接diauracycles，即，[金2 X 2（μ-P我镨2 CH 2 PPH 2）2 ]（X =氯，溴，I）和[金2（μ-P我镨2 CH 2 PPh 2）2 ] A 2 （A = CF 3 SO 3，ClO 4）。的
• Wolf, Justin; Manger, Matthias; Schmidt, Ulrich, Journal of the Chemical Society, Dalton Transactions, 1999, # 11, p. 1867 - 1875
  作者：Wolf, Justin、Manger, Matthias、Schmidt, Ulrich、Fries, Guido、Barth, Dietmar、Weberndoerfer, Birgit、Vicic, David A.、Jones, William D.、Werner, Helmut

  DOI：——

  日期：——