[Rh(η⁵-Cp*)(CH₂CH₂-n-C₄F₉)I(PMe₃)] | 1349737-50-3

• 英文名称: [Rh(η⁵-Cp*)(CH₂CH₂-n-C₄F₉)I(PMe₃)]
• 英文别名: [(η5-pentamethylcyclopentadienyl)RhI(CH2CH2nC4F9)(trimethylphosphine)]
• CAS: 1349737-50-3
• 化学式: C₁₉H₂₈F₉IPRh
• 分子量: 688.201
• InChiKey: BUBRODFDPIWGGD-UHFFFAOYSA-M

计算性质

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

反应信息

• 作为反应物：
  描述：

  [Rh(η⁵-Cp*)(CH₂CH₂-n-C₄F₉)I(PMe₃)] 、 silver trifluoromethanesulfonate 以 二氯甲烷-D2 为溶剂， 反应 2.0h， 生成 [Rh(η⁵-Cp*)(CH₂CH₂-n-C₄F₉)(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：

  1,1,2,2-四氢全氟己基碘 、 、 三甲基膦 以 甲苯 为溶剂， 反应 24.0h， 以26%的产率得到[Rh(η⁵-Cp*)(CH₂CH₂-n-C₄F₉)I(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

文献信息

• Reactions of Half-Sandwich Ethene Complexes of Rhodium(I) toward Iodoperfluorocarbons: Perfluoro-alkylation or -arylation of Coordinated Ethene versus Oxidative Addition
  作者：Juan Gil-Rubio、Juan Guerrero-Leal、María Blaya、José Vicente、Delia Bautista、Peter G. Jones

  DOI：10.1021/om2009588

  日期：2012.2.27

  respectively. Bridge splitting reactions of 1a, 1b, or 1c with phosphines afford complexes [Rh(η5-Cp*)(CH2CH2RF)I(PR3)] (3a, 3a′, 3c; RF = CF(CF3)2, R = iPr (3a″); RF = CF(CF3)CF2CF3, R = Me (3b), Ph (3b′)). In contrast, oxidative addition dominates over addition to ethene in the reactions of [Rh(η5-Cp*)(η2-C2H4)(PMe3)] with IRF (RF = CF2C6F5, nC3F7, nC4F9, CF═CF2) and in the reaction of [Rh(η5-Cp)(η2-C2H4)(PMe3)]

  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