3,4,8,9-tetramethyl-1,6-diphosphabicyclo(4.4.0)deca-3,8-diene | 1258870-28-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 磷环化合物
• 英文名称: 3,4,8,9-tetramethyl-1,6-diphosphabicyclo(4.4.0)deca-3,8-diene
• 英文别名: 2,3,7,8-Tetramethyl-1,4,6,9-tetrahydrodiphosphinino[1,2-a]diphosphinine；2,3,7,8-tetramethyl-1,4,6,9-tetrahydrodiphosphinino[1,2-a]diphosphinine
• CAS: 1258870-28-8
• 化学式: C₁₂H₂₀P₂
• 分子量: 226.238
• InChiKey: ROZZAFNEEQDKLJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  3,4,8,9-tetramethyl-1,6-diphosphabicyclo(4.4.0)deca-3,8-diene 在 三苯基硫化锑 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 1.08h， 生成
  参考文献：
  名称：

  Functionalization Reactions Characteristic of a Robust Bicyclic Diphosphane Framework

  摘要：

  The 3,4,8,9-tetramethy1-1,6-diphospha-bicyclo-[4.4.0]deca-3,8-diene (P-2(C6H10)(2)) framework containing a P-P bond has allowed for an unprecedented selectivity toward functionalization of a single phosphorus lone pair with reference to acyclic diphosphane molecules. Functionalization at the second phosphorus atom was found to proceed at a significantly slower rate, thus opening the pathway for obtaining mixed functional groups for a pair of P P bonded lambda(5)-phosphorus atoms. Reactivity with the chalcogen-atom donors MesCNO (Mes = 2,4,6-C6H2Me3) and SSIiPh(3) has allowed for the selective synthesis of the diphosphane chalcogenides OP2(C6H10)(2) (87%), O2P2(C6H10)(2) (94%), SP2(C6H10)(2) (56%), and S2P2(C6H10)(2) (87%). Computational studies indicate that the oxygen atom transfer reactions involve penta-coordinated phosphorus intermediates that have four membered {PONC} cycles. The P E bond dissociation enthalpies in EP2(C6H10)(2) were measured via calorimetric studies to be 134.7 +/- 2.1 kcal/mol for P-O, and 93 +/- 3 kcal/mol for P-S, respectively, in good agreement with the computed values. Additional reactivity with breaking of the P P bond and formation of diphosphinate O3P2(C6H10)(2) was only observed to occur upon heating of dimethylsulfoxide solutions of the precursor. Reactivity of diphosphane P2(C6H10)2 with azides allowed the isolation of monoiminophosphoranes (RN)P-2(C6H10)(2)(R = Mes, CPh3, SiMe3), and treatment with additional MesN3 yielded symmetric and unsymmetric diiminodiphosphoranes (RN)(MesN)P-2(C6H10)(2) (91% for R = Mes). Metalation reactions with the bulky dihninodiphosphorane ligand (MesN)(2)P-2(C6H10)(2) (nppn) allowed for the isolation and characterization of (rippn)Mo(n(3)-C3H5)Cl(CO)(2) (91%), (nppn)NiCl2 (76%), and [(nppn)Ni(eta(3)-2-C3H4Me)][OTf] showing that these ligands provide an attractive preorganized binding pocket for both late and early transition metals.

  DOI：

  10.1021/ic401052a
• 作为产物：
  描述：

  2,3-二甲基-1,3-丁二烯 在 phosphorus 作用下， 以 正己烷 为溶剂， 反应 14.0h， 以13.6%的产率得到3,4,8,9-tetramethyl-1,6-diphosphabicyclo(4.4.0)deca-3,8-diene
  参考文献：
  名称：

  将二磷单元光化学结合到有机分子中

  摘要：

  只需一次操作，即可从P 4 到有机二膦：含P 4且易于获得的1,3-二烯的溶液进行光解，一步一步生成无金属的双环有机二膦。使用2,3-二甲基丁二烯或1,3-丁二烯（参见附图）可以对二膦产物P 2（C 6 H 10）2和P 2（C 4 H 6）2进行分离和固态结构表征。

  DOI：

  10.1002/anie.201004385

文献信息

• Synthesis and Reactivity of Nickel-Stabilised μ² :η² ,η² -P₂ , As₂ and PAs Units
  作者：Gabriele Hierlmeier、Alexander Hinz、Robert Wolf、Jose M. Goicoechea

  DOI：10.1002/anie.201710582

  日期：2018.1.8

  The reactivity of two paramagnetic nickel(I) compounds, CpNi(NHC) (where Cp=cyclopentadienyl; NHC=1,3‐bis(2,4,6‐trimethylphenyl)imidazol‐2‐ylidene (IMes) or 1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene (IPr)), towards [Na(dioxane)x][PnCO] (Pn=P, As) is described. These reactions afford symmetric bimetallic compounds (μ2:η2,η2‐Pn2)Ni(NHC)(CO)}2. Several novel intermediates en route to such species

  两种顺磁性镍（I）化合物CpNi（NHC）（其中Cp =环戊二烯基; NHC = 1,3-双（2,4,6-三甲基苯基）咪唑-2-亚烷基（IMes）或1,3-描述了朝向[Na（dioxane ）x ] [PnCO]（Pn = P，As）的双（2,6-二异丙基苯基）咪唑-2-亚基（IPr））。这些反应得到对称的双金属化合物（μ 2：η 2，η 2 -Pn 2）的Ni（NHC）（CO）} 2。几个新的中间体途中这种物质被鉴定和表征，包括含有所述PCO的化合物-在前所未有的μ阴离子2 η：2，η 2 -结合模式。最终，在治疗的（μ 2：η 2，η 2 -Pn 2）的Ni（IMES）（CO）} 2种化合物与一氧化碳中，PN 2单元可被释放，得到P 4在含磷物质的情况下，和元素砷的情况下（μ 2：η 2，η 2 -As 2）的Ni（IMES）（CO）} 2。
• Cobalt Complexes Supported by <i>cis</i>-Macrocyclic Diphosphines: Synthesis, Reactivity, and Activity toward Coupling Carbon Dioxide and Ethylene
  作者：Ioana Knopf、Marc-André Courtemanche、Christopher C. Cummins

  DOI：10.1021/acs.organomet.7b00734

  日期：2017.12.26

  The coordination chemistry of cis-macrocyclic diphosphines readily accessed from white phosphorus was explored, with a focus on preparing and studying cobalt complexes. cis-1,6-Dicyclohexyl-3,4,8,9-tetramethyl-2,5,7,10-tetrahydro-1,6-DiPhospheCine, or Cy2–DPC (1), was primarily used as a model diphosphine. Cobalt(II) dihalide diphosphine complexes such as (Cy2–DPC)CoX2, X = Cl (2) and I (3), were prepared

  探索了易于从白磷中获得的顺式-大环二膦的配位化学，重点是制备和研究钴配合物。cis -1,6-Dicyclohexyl-3,4,8,9-tetramethyl-2,5,7,10-tetrahydro-1,6-DiPhospheCine或Cy 2 –DPC（1），主要用作模型二膦。制备了（Cy 2 -DPC）CoX 2，X = Cl（2）和I（3）等二卤化钴（II）二膦配合物，并研究了其对多种还原剂的反应性。我们成功地制备了不寻常的碘桥联钴（I）二聚体[（Cy 2 –DPC）CoI] ，并进行了结构表征。2（8）。还研究了这些钴配合物，作为潜在的催化剂，用于二氧化碳和乙烯的偶联反应，以生产丙烯酸酯（一种有价值的聚合物前体）。尽管还没有催化作用，但是已经报道了能够介导这种转化的钴配合物的第一个例子。值得注意的是，还发现众所周知的商业配合物ClCo（PPh 3）3在介导丙烯酸酯生产中也具有活性。
• Photochemical Incorporation of Diphosphorus Units into Organic Molecules
  作者：Daniel Tofan、Christopher C. Cummins

  DOI：10.1002/anie.201004385

  日期：——

  From P4 to organic diphosphanes in a single operation: Photolysis of solutions containing P4 and readily available 1,3‐dienes produces bicyclic organic diphosphanes, in a one‐step, metal‐free protocol. Use of 2,3‐dimethylbutadiene or 1,3‐butadiene (see drawing) allowed the isolation and solid‐state structural characterization of the diphosphane products P2(C6H10)2 and P2(C4H6)2.

  只需一次操作，即可从P 4 到有机二膦：含P 4且易于获得的1,3-二烯的溶液进行光解，一步一步生成无金属的双环有机二膦。使用2,3-二甲基丁二烯或1,3-丁二烯（参见附图）可以对二膦产物P 2（C 6 H 10）2和P 2（C 4 H 6）2进行分离和固态结构表征。
• Bicyclic dinuclear tris-(ditopic diphosphane) complexes of zerovalent group 10 metals
  作者：Daniel Tofan、Christopher C. Cummins

  DOI：10.1039/c2sc20559a

  日期：——

  Selective formation of bimetallic group 10 complexes using the Cs symmetric, bicyclic diphosphane P2C12H20 is reported herein. With its eclipsed lone pairs disposed at a relative angle of ca. 45°, the diphosphane framework is ideally suited to form multiple bridges between two metal centers. The complexes contain M2P6} cages with three diphosphane bridges and a pair of trans-axial ligands such as EPh3 (E = P, As, Sb) or η1-P2C12H20. X-Ray crystallography experiments revealed that the cages have a pseudo-D3h symmetry, with metal–metal distances in the 3.9–4.1 Å range. The complexes were isolated in 48–91% yield as crystalline, bright yellow or orange powders. Substitution of the axial ligands with the M2P6} cages remaining intact was also observed.

  本文报告了利用铯对称双环二膦烷 P2C12H20 选择性地形成第 10 组双金属配合物的情况。由于二膦烷框架中的孤对以约 45° 的相对角度存在，因此非常适合在两个金属中心之间形成多桥。这些配合物包含具有三个二膦桥的M2P6}笼和一对跨轴配体，如 EPh3（E = P、As、Sb）或 η1-P2C12H20。X 射线晶体学实验显示，笼具有假 D3h 对称性，金属与金属之间的距离在 3.9-4.1 Å 范围内。这些配合物以 48-91% 的产率分离出来，呈亮黄色或橙色结晶粉末状。此外，还观察到轴向配体被取代，而M2P6}笼保持完整。
• Frustrated Lewis Pair Adduct of Atomic P(−1) as a Source of Phosphinidenes (PR), Diphosphorus (P ₂ ), and Indium Phosphide
  作者：Brandon L. Frenette、Jonathan Trach、Michael J. Ferguson、Eric Rivard

  DOI：10.1002/anie.202218587

  日期：2023.3

  A frustrated Lewis pair (FLP) chelation approach was employed to access low-valent phosphorus centers. The resulting adducts act as P atom sources for phosphinidene (PR) transfer, indium phosphide synthesis, and neutral P2 transfer to organic substrates.

  采用受挫路易斯对 (FLP) 螯合方法来访问低价磷中心。所得加合物作为磷亚胺 (PR) 转移、磷化铟合成和中性 P 2转移至有机底物的 P 原子源。