dpmppp | 1375111-64-0

• 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: dpmppp
• 英文别名: meso-1,3-bis[(diphenylphosphinomethyl)phenylphosphino]propane
• CAS: 1375111-64-0
• 化学式: C₄₁H₄₀P₄
• 分子量: 656.6
• InChiKey: MDLOSRIVYPSJGT-YQOBSMRKSA-N

物化性质

• 沸点：
  743.5±55.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9
• 重原子数：
  45
• 可旋转键数：
  14
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.12
• 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：

  二氯甲烷 、 dichloro(cycloocta-1,5-diene)palladium (II) 、 dpmppp 以 二氯甲烷 为溶剂， 以75%的产率得到[PdCl2(meso-1,3-bis[(diphenylphosphinomethyl)phenylphosphino]propane)]*0.75dichloromethane
  参考文献：
  名称：

  Cyclic Trinuclear Rh₂M Complexes (M = Rh, Pt, Pd, Ni) Supported by meso-1,3-Bis[(diphenylphosphinomethyl)phenylphosphino]propane

  摘要：

  Reaction of [MCl2(cod)] (M = Pd, Pt) with a tetraphosphine, meso-1,3-bis[(diphenylphosphinomethyl)phenylphosphino]propane (dpmppp), afforded the mononuclear complexes [MCl2(dpmppp)] (M = Pd (3a), Pt (3b)), in which the dpmppp ligand coordinated to the M ion by two inner phosphorus atoms to form a six-membered chelate ring with two outer phosphines uncoordinated. The pendant outer phosphines readily reacted with [RhCl(CO)(2)](2) to give the cationic heterotrinuclear complexes [MRh2(mu-Cl)(3)(mu-dpmppp) (CO)(2)]X (X = [RhCl(CO)(2)](2), M = Pd (4a), Pt (4b); X = PF6, M = Pd (5a), Pt (5b)). The nickel analogue [NiRh2(mu-Cl)(3)(mu-dpmppp)(CO)(2)]PF6 (5c) was also prepared. A neutral homotrinuclear Rh-3 complex, [Rh-3(mu-Cl)(3)(mu-dpmppp)(CO)(2)] (6), was synthesized by the reaction of [RhCl(CO)(2)](2) with dpmppp and was further reacted with HgX2 (X = Cl, Br, I) to afford the Rh3Hg tetranuclear complexes [Rh-3(HgX)(mu-Cl)(2)(mu-X)(mu-dpmppp)(CO)(2)]PF6 (X = Cl (7a), Br (7b), I (7c)), where the Rh-3(mu-Cl)(2)(mu-X) cores act as tridentate ligands to form three donor-acceptor Rh -> Hg interactions. The two CO ligands of 7a-c were replaced by XylNC to yield [Rh-3(HgX)(mu-Cl)(2)(mu-X)(mu-dpmppp)(XylNC)(2)]PF6 (X = Cl (8a), Br (8b), I (8c)). The isocyanides had an appreciable influence on the three Rh -> Hg interactions, which was monitored by the (2)J(Hgp) values observed in the P-31{H-1} NMR spectra and discussed on the basis of DFT calculations. Complex 6 also reacted with CuCl and HBF4 to give [Rh-3(CuCl)(mu-Cl)(3)(mu-dpmppp)(CO)(2)] (9) and [Rh-3(mu(3)-H)(mu-Cl)(3)(mu-dpmppp)(CO)(2)]BF4 (10), respectively. These results suggested that the new tetraphosphine dpmppm proved quite useful in constructing fine-tunable heterometallic frameworks.

  DOI：

  10.1021/om300278k

文献信息

• Synergistic Cu₂ Catalysts for Formic Acid Dehydrogenation
  作者：Takayuki Nakajima、Yoshia Kamiryo、Masayo Kishimoto、Kaho Imai、Kanako Nakamae、Yasuyuki Ura、Tomoaki Tanase

  DOI：10.1021/jacs.9b03532

  日期：2019.6.5

  using a new linear tetraphosphine, meso-Ph2PCH2P(Ph)(CH2)4P(Ph)CH2PPh2 ( meso-L4), and were converted into active catalysts of [Cu2(μ-O2CH)( meso-L4)(RNC)2]+ under the reaction conditions of formic acid dehydrogenation, where unsymmetric dinuclear copper sites supported by the tetradentate phosphine and isocyanide ligands were essential to demonstrate effective catalytic activity.

  六核氢化铜配合物 [Cu6(μ3-H)2(meso-L4)3(RNC)4](PF6)4 (R = tBu (6a), Cy (6b)) , meso-Ph2PCH2P(Ph)(CH2)4P(Ph)C Ph2 (meso-L4)，并在反应条件下转化为[Cu2(μ-O2CH)(meso-L4)(RNC)2]+的活性催化剂甲酸脱氢，其中由四齿膦和异氰化物配体支持的不对称双核铜位点对于证明有效的催化活性至关重要。
• Oxidative addition of an aromatic ortho C–H bond of tetraphosphine to asymmetric diiridium(<scp>i</scp>) centres
  作者：Takayuki Nakajima、Sayo Noda、Miyuki Sakamoto、Aya Matsui、Kanako Nakamae、Bunsho Kure、Yasuyuki Ura、Tomoaki Tanase

  DOI：10.1039/c5dt04725k

  日期：——

  X-ray crystallography and DFT calculations as an electron-deficient 32e− IrI2 species involving a IrI→IrI dative bond (2.7989(5) Å). The reaction pathways from 6 to 2 were investigated by DFT calculations. The present study suggested that a novel oxidative addition of an ortho C–H bond proceeded on the cis/trans-P,P asymmetric diiridium(I) scaffold supported by the tetraphosphine, dpmppp, which was

  一个tetraphosphine的反应，内消旋-二[（二苯基膦基）苯基]膦基}丙烷（dpmppp）中，用[的IrCl（COD）] 2和CO（1大气压）或胩（RNC）在NH 3的存在下4 PF 6在80-100℃下，在二氯甲烷/乙腈/丙酮和/或甲醇的混合溶剂，得到不对称的二铱（II）配合物，物[Ir 2（H）（Cl）的（μ-（dpmppp-H）-κ P 4 ç）（CO ）3 ] PF 6（1）和物[Ir 2（H）（μ-（dpmppp-H）-κ P 4 ç）（RNC）4）] - （PF 6）2（R = 2,6-二甲苯基（2），2,4,6-甲磺酰基（3）; dpmppp-H = PPh（o -C 6 H 4）CH 2 P（Ph）（CH 2）3 P（ Ph）CH 2 PPh 2 } -）。用类似的反应吨BuNC导致单核Ir中形成III复合物的[Ir（H）（dpmppp-κ P 3）（吨BuNC）2
• Reversible dioxygen binding on asymmetric dinuclear rhodium centres
  作者：Takayuki Nakajima、Miyuki Sakamoto、Sachi Kurai、Bunsho Kure、Tomoaki Tanase

  DOI：10.1039/c3cc41815d

  日期：——

  Electron-deficient dinuclear rhodium complexes [Rh2Cl2(μ-dpmppp)(RNC)] (1), with the linear tetraphosphine ligand dpmppp, showed reversible binding of molecular oxygen to form asymmetric dirhodium η2-peroxo complexes [Rh2Cl2(O2)(μ-dpmppp)(RNC)] (2) stabilized by a Rh→Rh dative bond.

  具有线性四膦配体 dpmppp 的缺电子二核铑配合物 [Rh2Cl2(μ-dpmppp)(RNC)] (1)显示出与分子氧的可逆结合，形成由 Rh→Rh 二价键稳定的不对称η2-过氧二铑配合物 [Rh2Cl2(O2)(μ-dpmppp)(RNC)] (2)。
• Tri- and Tetranuclear Copper Hydride Complexes Supported by Tetradentate Phosphine Ligands
  作者：Takayuki Nakajima、Yoshia Kamiryo、Kanae Hachiken、Kanako Nakamae、Yasuyuki Ura、Tomoaki Tanase

  DOI：10.1021/acs.inorgchem.8b01628

  日期：2018.9.4

  synthesize a new series of tri- and tetranuclear copper hydride complexes. Reactions of meso-dpmppe or meso-dpmppp with CuCl/NH4PF6 or [Cu(CH3CN)4]PF6 in the presence of NaBH4 afforded trinuclear copper hydride complexes, [Cu3(μ3-H)(meso-dpmppe)2](PF6)2 (1) and [Cu3(μ3-H)(meso-dpmppp)2](PF6)2 (2), while a similar reaction with rac-dpmppe resulted in the formation of a tetranuclear copper dihydride complex

  三种类型的四齿膦配位体的具有不同中心亚甲基链和配置，内消旋-和外消旋-Ph 2 PCH 2 P（PH）（CH 2）Ñ P（PH）CH 2 PPH 2（Ñ = 2，内消旋-和外消旋- dpmppe；n = 3，内消旋-dpmppp）用于合成一系列新的三核和四核氢化铜配合物。中观-dpmppe或中观-dpmppp与CuCl / NH 4 PF 6或[Cu（CH 3 CN）4] PF 6中的NaBH存在4，得到三核铜氢化物络合物，[铜3（μ 3 -H）（内消旋-dpmppe）2 ]（PF 6）2（1）和[铜3（μ 3 -H）（内消旋-dpmppp）2 ]（PF 6）2（2），而具有类似的反应外消旋-dpmppe导致了四核二氢化铜配合物，[在该Cu 4（μ 3 -H）2（外消旋-dpmppe）2]（PF 6）2（5）。配合物1和5与RNC进一步反应（R =吨卜中，Cy，的Xyl），得到[铜3（μ 3
• Unsymmetric Dinuclear Rh^I₂ and Rh^IRh^III Complexes Supported by Tetraphosphine Ligands and Their Reactivity of Oxidative Protonation and Reductive Dechlorination
  作者：Takayuki Nakajima、Mami Maeda、Aya Matsui、Mariko Nishigaki、Momoko Kotani、Tomoaki Tanase

  DOI：10.1021/acs.inorgchem.1c03278

  日期：2022.1.17

  to reveal two reaction pathways depending on the terminal auxiliary ligand L. Further, the reductive dechlorination converting RhIRhIII (4b,d) to RhI2 (1b,d) was accomplished with a CO terminal ligand by reacting with various amines that acted as one-electron reducing agents through an inner-sphere electron transfer mechanism. DFT calculations were performed to elucidate the electronic structures of

  两个线性四齿膦配体，meso -Ph 2 PCH 2 P(Ph)CH 2 X CH 2 P(Ph)CH 2 PPh 2 ( X = CH 2 ( meso -dpmppp), NBn ( meso -dpmppmNBn; Bn = 苄基) ) 用于合成不对称双核 Rh I配合物 [Rh 2 Cl 2 ( meso -dpmppp)(L)] (L = XylNC ( 1a ), CO ( 1b )) 和 [Rh 2 Cl 2 ( meso -dpmppmNBn)( L)] (L = XylNC (1c ), CO ( 1d ))，其中缺电子的 Rh I → Rh I中心与 30 个价电子由四膦以不寻常的顺式/反式-P ,P配位模式支持。1a – d的 Rh I二聚体在空气中用 HCl 处理，得到 Rh I → Rh III二聚体，其中 32 e – [Rh 2 Cl 4 ( meso -dpmppp)(L)]