bis(pentafluoroethyl)methylphosphine | 197703-75-6

• 分子结构分类: 有机化合物 - 有机磷化合物 - 磷芥子化合物
• 英文名称: bis(pentafluoroethyl)methylphosphine
• 英文别名: (C2F5)2P(methyl)；Phosphine, methylbis(pentafluoroethyl)-；methyl-bis(1,1,2,2,2-pentafluoroethyl)phosphane
• CAS: 197703-75-6
• 化学式: C₅H₃F₁₀P
• 分子量: 284.037
• InChiKey: FOTJIBCFYOPXFX-UHFFFAOYSA-N

物化性质

• 沸点：
  71.6±40.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  bis(pentafluoroethyl)methylphosphine 以 氟磺酸 为溶剂， 生成 trans-[(C2F5)2P(methyl)]2Pt(methyl)(OSO2F)
  参考文献：
  名称：

  [（C 2 F 5）2 MeP] 2 Pt（Me）X（X = Me，O 2 CCF 3，OTf，OSO 2 F）的合成和反应性：与螯合物受体类似物的反应性比较

  摘要：

  新型铂甲基配合物cis-（dfmp）2 Pt（Me）2和反式-（dfmp）2 Pt（Me）X的比较研究（dfmp =（C 2 F 5）2 MeP; X = O 2 CCF 3， OTf，OSO 2 F）与先前报道的受体螯合物类似物（dfepe）Pt（Me）X（dfepe =（C 2 F 5）2 PCH 2 CH 2 P（C 2 F 5）2 ; X = Me，O 2 CCF 3，OTf，OSO 2F）被提出。与对H 2和CO均呈惰性的（dfepe）Pt（Me）2相比，顺式（dfmp）2 Pt（Me）2容易反应形成（dfmp）4 Pt和顺式（dfmp）（分别为CO）Pt（Me）2。同样，（dfepe）Pt（Me）2在高达180°C的温度下仍稳定，而顺式（dfmp）2 Pt（Me）2在80°C的苯-d 6中的热分解导致乙烷还原消除并生成（ dfmp）4分。溶解顺式-（dfmp）2 Pt（Me）2

  DOI：

  10.1021/om034228h

文献信息

• Acceptor PCP Pincer Iridium Chemistry: (^CF_<b>3</b>PCP)Ir^III Coordination Properties
  作者：Jeramie J. Adams、Ade Lau、Navamoney Arulsamy、Dean M. Roddick

  DOI：10.1021/om1008633

  日期：2011.2.28

  syntheses of Ir(I) and Ir(III) complexes incorporating the electron-poor pincer ligand (1,3-C6H3(CH2P(CF3)2)2) (CF3PCP) are reported. Under mild conditions, the reaction of CF3PCPH with [(cod)Ir(μ-Cl)]2 in benzene gave polymeric [(cod)IrCl(μ-CF3PCPH)]n, which was structurally characterized. Thermolysis of [(coe)2Ir(μ-Cl)]2 or [(cod)Ir(μ-Cl)]2 with CF3PCPH in toluene at 120 °C resulted in metalation to give

  报道了掺有贫电子钳式配体（1,3-C 6 H 3（CH 2 P（CF 3）2）2）（CF 3 PCP）的Ir（I）和Ir（III）配合物的合成。在温和条件下，反应CF 3 PCPH与[（COD）的Ir（μ-Cl）的] 2在苯，得到聚合物[（COD）的IrCl（μ- CF 3 PCPH）] Ñ，其在结构上表征。[（coe）2 Ir（μ-Cl）] 2或[（cod）Ir（μ-Cl）] 2用CF 3的热分解120°C的甲苯中的PCPH导致金属化，生成的不是预期的16电子（CF 3 PCP）Ir（H）Cl产物，而是配位饱和的CF 3 PCPH桥联二聚体（CF 3 PCP）Ir（H） CL} 2（μ- CF 3 PCPH）。容易置换桥接的CF 3 PCPH配体，以提供单体产物（CF 3 PCP）Ir（L）（H）Cl（L = CO，MeCN）; （CF 3 PCP）Ir（L）（H）Cl（L = CO，MeCN，PhCN，C
• Acceptor PCP Pincer Iridium(I) Chemistry: Stabilization of Nonmeridional PCP Coordination Geometries
  作者：Jeramie J. Adams、Navamoney Arulsamy、Dean M. Roddick

  DOI：10.1021/om100864g

  日期：2011.2.28

  of a series of four-coordinate complexes (CF3PCP)Ir(L) (L = CO, DBU, nbe, coe, MeP(C2F5)2 (dfmp)) and five-coordinate complexes (CF3PCP)Ir(L)(L′) (L = L′ = CO, dfmp, nbd, cod, (C2F5)2PCH2CH2P(C2F5)2 (dfepe); L = PhCN, L′ = C2H4) from dehydrohalogenation of (CF3PCP)Ir(C2H4)(H)Cl with Et3N in the presence of trapping ligands is reported. (CF3PCP)Ir(L) and (CF3PCP)Ir(L)2 for L = CO, dfmp have been structurally

  制备一系列四坐标配合物（CF 3 PCP）Ir（L）（L = CO，DBU，nbe，coe，MeP（C 2 F 5）2（dfmp））和五坐标配合物（CF 3 PCP）Ir（L）（L'）（L = L'= CO，dfmp，nbd，cod，（C 2 F 5）2 PCH 2 CH 2 P（C 2 F 5）2（dfepe）; L = PhCN （CF 3 PCP）Ir（C 2 H 4）（H）Cl与Et 3的脱卤化氢，L'= C 2 H 4）据报道，N存在于俘获配体中。（CF 3 PCP）Ir（L）和（CF 3 PCP）Ir（L）2（对于L = CO，dfmp）已进行结构表征，并建立了（CF 3 PCP）Ir（L）的扭曲三角双锥体配位几何2具有弯曲的PCP单元和不等的轴向和赤道L坐标位置。（CF 3 PCP）Ir（L）（L'）系统（L = L'= CO，C 2 H 4 ; L = PhCN，L'= C
• Structural and reactivity properties of perfluoroalkylphosphine complexes of platinum(0)
  作者：Jennifer Phelps、Jeffrey L. Butikofer、Bhusan Thapaliya、Eric Gale、Courtney L. Vowell、Suman Debnath、Navamoney Arulsamy、Dean M. Roddick

  DOI：10.1016/j.poly.2016.04.045

  日期：2016.9

  CF3CO2H to (dfebp)2Pt generates the expected Pt(II) trans-(dfebp)2Pt(O2CCF3)(H) product, while treatment with the mesitylenium acid (C6Me3H4)+B(C6F5)4− leads to phosphine loss and formation of the arene complex [(η6-C6Me3H3)Pt(dfebp)(H)]+(B(C6F5)4)−. Addition of ethylene to (dfebp)2Pt results in facile and reversible equilibria with the ethylene adducts (dfebp)2Pt(C2H4) and (dfebp)Pt(C2H4)2, which have

  摘要报道了具有π-受体全氟烷基膦配体（PFAP's）的2和3配位的Pt（0）配合物的合成和结构表征。（dfebp）2Pt（dfebp =（C2F5）2PtBu）可以通过在纯dfebp中热解（cod）Pt（Ph）2或通过更有效地通过用2当量的（nbe）3Pt处理而以中等收率制备。在H2存在下的dfebp。加1当量 CF3CO2H转化为（dfebp）2Pt会生成预期的Pt（II）反式-（dfebp）2Pt（O2CCF3）（H）产物，而用间苯二酸（C6Me3H4）+ B（C6F5）4-进行处理会导致磷化氢损失并形成芳烃配合物[（η6-C6Me3H3）Pt（dfebp）（H）] +（B（ ）4）-。在（dfebp）2Pt中添加乙烯会导致与乙烯加成物（dfebp）2Pt（C2H4）和（dfebp）Pt（ ）2形成容易且可逆的平衡，已通过VT NMR光谱法对其进行了定量。
• Investigation of Iridium^CF₃PCP Pincer Catalytic Dehydrogenation and Decarbonylation Chemistry
  作者：Jeramie J. Adams、Navamoney Arulsamy、Dean M. Roddick

  DOI：10.1021/om2011886

  日期：2012.2.27

  The iridium fluorinated pincer complex ((PCP)-P-CF3)Ir-(cod) ((PCP)-P-CF3 = 2,6-C6H3(CH2P(CF3)(2))(2)) catalyzes hydrogen transfer from cyclooctane (coa) to tert-butylethylene (tbe) in 1/1 coa/tbe at 200 degrees C to give cyclooctene (coe) and neohexane (tba) at an initial rate of 40 TO h(-1). In 5/1 coa/tbe, higher initial activity (155 TO h(-1)) and higher turnovers (2580 TON's after 1450 min) are found. Samples of 95% the contain significant amounts of isoprene (2-methyl-1,3-butadiene), which reacts with ((PCP)-P-CF3)Ir(cod) to initially form ((PCP)-P-CF3)Ir(isoprene). Alkene inhibition studies show that ((PCP)-P-CF3)Ir is only modestly inhibited (67% reduced initial activity) in the presence of 800 equiv of added coe. Unlike donor pincer systems, no decrease in activity is noted under 1 atm of N-2 or in the presence of excess water. Hydrogenation of ((PCP)-P-CF3)Ir(L) (L = cod, isoprene) did not produce ((PCP)-P-CF3)Ir(H)(x) but instead afforded the first example of the unusual aryl-bridged bimetallic complex [(mu-1 kappa(2)(P,C),2 kappa(2)(P',C)-(PCP)-P-CF3)Ir(H)(2)](2)(mu-(PCPH)-P-CF3)(mu-H), which has been isolated and crystallographically characterized. Ir(I) pincer complexes ((PCP)-P-CF3)Ir(L) (L = MeP(C2F5)(2), CO, dfepe (dfepe = (C2F5)(2)PCH2CH2P(C2F5)(2))) also serve as moderately active aldehyde decarbonylation catalyst precursors for 2-naphthaldehyde with similar activities in diglyme (1.7 TO h(-1), 152 degrees C) and in 1,4-dioxane (0.052 TO h(-1), 94 degrees C). The catalyst resting states are the corresponding five-coordinate carbonyl complexes ((PCP)-P-CF3)Ir(MeP(C2F5)(2))(CO), ((PCP)-P-CF3)Ir(CO)(2), and [((PCP)-P-CF3)Ir-(CO)](2)(mu-dfepe) (CO)](2)(mu-dfepe). DFT studies indicate that the preferred catalyst resting state for alkane dehydrogenation, ((PCP)-P-CF3)Ir-(cod), can be ascribed to the lower steric requirements of the CF3-substituted pincer ligand.
• Adduct Studies and Reactivity of <i>trans</i>-[(C₂F₅)₂MeP]₂Pt(Me)X (X = O₂CCF₃, OTF, OSO₂F)
  作者：Jeffrey L. Butikofer、Thomas G. Parson、Dean M. Roddick

  DOI：10.1021/om060847p

  日期：2006.12.1

  The comparative reactivity properties of previously reported trans-(dfmp)(2)Pt(Me)X (dfmp = (C2F5)(2)-MeP; X = O2CCF3, OTf, OSO2F) with small molecules are presented. Anionic ligand displacement by CO depends upon X and the corresponding acid solvent. In trifluoroacetic acid, treatment of trans(dfmp)(2)Pt(Me)(O2CCF3) with CO results in loss of dfmp to form the mixed phosphine/carbonyl product (dfmp)(CO)Pt(Me)(O2CCF3). However, in triflic and fluorosulfonic acids trans-(dfmp)(2)Pt(Me)(X) compounds react with CO to form trans-(dfmp)(2)Pt(Me)(CO)(+)(X)(-). trans-(dfmp)(2)Pt(Me)(X) systems react with H-2 under both acidic and aprotic conditions to form trans-(dfmp)(2)Pt(H)(X); trans-(dfmp)(2)Pt(H)(OTf) has been crystallographically characterized. Treatment of trans-(dfmp)(2)Pt(H)(OTf) with CO or dfmp gives trans-(dfmp)(2)Pt(H)(CO)(+) or (dfmp)(3)Pt(H)(+), respectively. In contrast to trans-(dfmp)(2)Pt(Me)(OTf), which releases methane in HOTf, trans-(dfmp)(2)Pt(Me)(OSO2F) in FSO3H at 80 degrees C cleanly produces the reductive elimination product MeOSO2F. Carbonylation of trans-[(dfmp)(2)PtMe(CO)]X-+(-) under 1000 psi CO in turn cleanly produces MeC(O)X at ambient temperatures. The mechanism of reductive elimination from these Pt(II) precursors is discussed.