[(η5-pentamethylcyclopentadienyl)RhI(CH2CH2nC3F7)(trimethylphosphine)] | 1349737-49-0

• 英文名称: [(η5-pentamethylcyclopentadienyl)RhI(CH2CH2nC3F7)(trimethylphosphine)]
• CAS: 1349737-49-0
• 化学式: C₁₈H₂₈F₇IPRh
• 分子量: 638.193
• InChiKey: XHRYPSGYPZKBPN-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [(η5-pentamethylcyclopentadienyl)RhI(CH2CH2nC3F7)(trimethylphosphine)] 、 silver trifluoromethanesulfonate 以 二氯甲烷-D2 为溶剂， 反应 2.0h， 生成 [Rh(η⁵-Cp*)(CH₂CH₂-i-C₃F₇)(OTf)(PMe₃)]
  参考文献：
  名称：

  Rh（I）和Ir（I）配合物中配位乙烯的全氟烷基化。碘氟代烷烃到乙烯的催化加成

  摘要：

  The complexes [M(eta(5)-CP*)(eta(2)-C2H4)(2)] (M = Rh, Ir) react with iodoperfluoroalkanes to give [M(eta(5)-Cp*)(CH2CH2RF)(mu-I)](2) (main product) and (CH2CH2RF)(mu-I)(2)M(eta(5)-Cp*)I] (RF = t-C4F9, M = Ir; R-F = c-C6F11, M = Ir, Rh). Similarly, the complexes [M(eta(5)-Cp*)(eta(2)-C2H4)(PPh3)] react with iodoperfluoroalkanes to give [M(eta(5)-Cp*)(CH2CH2RF)I(PPh3)] (M = Ir, R-F = t-C4F9, i-C3F7; M = Rh, R-F = t-C4F9). Evidence for the generation of the heptafluoroisopropyl carbanion in the reaction of [Ir(eta(5)-Cp*)(eta(2)-C2H4)(PPh3)] with I-i-C3F7 was obtained, which suggests that the reaction is initiated by the transfer of two electrons from the Ir(I) complex to the iodoperfluoroalkane. The iodo-bridged complexes react with PPh3 to give [M(eta(5)-Cp*)(CH2CH2RF)I(PPh3)] (M = Ir, R-F = t-C4F9; c-C6F11; M = Rh, R-F = c-C6F11). The complexes [Ir(eta(5)-Cp*)(CH2CH2RF)I(PPh3)] (RF = c-C6F11, i-C3F7) react with AgOTf to give [Ir(eta(5)-Cp*)H(eta(2)-CH2=CHRF)(PPh3)]OTf. The analogous reaction of [Ir(eta(5)-Cp*)(CH2CH2-t-C4F9)I(PPh3)] gives CH3CH2-t-C4F9 and [Ir(eta(5)-Cp*)(eta(2)-o-C6H4PPh2)]OTf, which reacts with PPh3 to give [Ir(eta(5)-Cp*)(eta(2)-o-C6H4PPh2)(PPh3)]OTf. This cyclometalated complex and its analogue [Ir(eta(5)-Cp*)(eta(2)-o-C6H4PPh2)(P(p-Tol)(3))]OTf are also prepared by the reaction of [Ir(eta(5)-Cp*)(Me)Cl(PPh3)] with AgOTf and PPh3 or P(p-Tol)(3). The derivatives [Ir(eta(5)-Cp*)(CH2CH2RF)(PPh3)L]OTf (L = CO, R-F = c-C6F11; i-C3F7; L = PPh3, R-F = i-C3F7) are isolated in the reactions of the Ir hydrido alkene complexes with CO or PPh3.The reactions of [Rh(eta(5)-Cp*)(CH2CH2RF)I(PR3)] (R = Me, R-F = i-C3F7, n-C4F9, t-C4F9; R = Ph, RF = i-C3F7, t-C4F9, c-C6F11) with AgOTf afford unstable triflato complexes that decompose to give CH2=CHRF, but in the presence of PR3 the complexes [Rh(eta(5)-Cp*)(CH2CH2RF)(PR3)(2)]OTf (R = Ph, R-F = i-C3F7; t-C4F9, c-C6F11; R = Me, R-F = i-C3F7, t-C4F9) were formed. When R = Ph, these complexes are unstable and decompose quantitatively to give [Rh(eta(5)-Cp*)H(PPh3)(2)]OTf and CH2=CHRF. Complexes of the type [M(eta(5)-Cp*)(eta(2)-C2H4)(2)] (M = Rh, Ir) and [Rh(eta(5)-Cp*)(CH2CH2RF)I(L)] are initiators for the radical addition of IRF to ethene.

  DOI：

  10.1021/acs.organomet.6b00929
• 作为产物：
  描述：

  (η5-pentamethylcyclopentadienyl)Rh(ethylene)2 、 七氟-1-碘丙烷 、 三甲基膦 以 氘代苯 为溶剂， 生成 [(η5-pentamethylcyclopentadienyl)RhI2(trimethylphosphine)] 、 [(η5-pentamethylcyclopentadienyl)RhI(nC3F7)(trimethylphosphine)] 、 [(η5-pentamethylcyclopentadienyl)RhI(CH2CH2nC3F7)(trimethylphosphine)]
  参考文献：
  名称：

  铑（I）的半三明治乙烯络合物对碘代氟化碳的反应：配位乙烯的全氟烷基化或芳基化与氧化加成

  摘要：

  全氟烷基化或协调的乙烯的perfluoroarylation时发生复合物的[Rh（η 5 -Cp *）（η 2 -C 2 H ^ 4）2 ]或[铑（η 5 -Cp *）（η 2 -C 2 H ^ 4）（ PR 3）]与IR反应˚F，得到复合物的[Rh（η 5 -Cp *）（CH 2 CH 2 - [R ˚F）（μ-I）] 2（R ˚F = CF（CF 3）2（1A）， CF（CF 3）CF 2 CF 3（图1b），或C（CF 3）3（1C））和[（η 5 -Cp *）IRH（μ-I）2的Rh（η 5 -Cp *）（CH 2 CH 2 - [R ˚F）]（2A - ç），或铑[Rh（η 5 -Cp *）（CH 2 CH 2 - [R ˚F）I（PR 3）]（R =我，R ˚F = CF（CF 3）2（图3a），C（CF 3）3（3c），C 6 F 5（3d）; R ＝ Ph，RF＝ CF（CF

  DOI：

  10.1021/om2009588