[(C5(CH3)5)(P(CH3)3)Rh(CH3)(dichloromethane)][B(3,5-C6H3(CF3)2)4] | 431882-00-7

• 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: [(C5(CH3)5)(P(CH3)3)Rh(CH3)(dichloromethane)][B(3,5-C6H3(CF3)2)4]
• 英文别名: [(η5-C5Me5)(PMe3)Rh(III)(Me)(CH2Cl2)]B(3,5-(CF3)2C6H3)4；[Cp(*)Rh(Me)(PMe3)ClCH2Cl]BAr'4；carbanide;dichloromethane;1,2,3,4,5-pentamethylcyclopenta-1,3-diene;rhodium(3+);tetrakis[3,5-bis(trifluoromethyl)phenyl]boranuide;trimethylphosphane
• CAS: 431882-00-7
• 化学式: C₁₅H₂₉Cl₂PRh*C₃₂H₁₂BF₂₄
• 分子量: 1277.4
• InChiKey: HFSFZAAQJBEUKH-UHFFFAOYSA-N

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：

  [(C5(CH3)5)(P(CH3)3)Rh(CH3)(dichloromethane)][B(3,5-C6H3(CF3)2)4] 、 三苯基硅烷 以 二氯甲烷 为溶剂， 以99%的产率得到[(C5(CH3)5)(P(CH3)3)Rh(Si(C6H5)3)(dichloromethane)][B(3,5-C6H3(CF3)2)4]
  参考文献：
  名称：

  Carbon−Carbon Bond Activation of R−CN (R = Me, Ar, ⁱPr, ^tBu) Using a Cationic Rh(III) Complex

  摘要：

  Addition of 1.0 equiv of Ph3SiH to [Cp*(PMe3)Rh(Me)(CH2Cl2)]+BAr'4- (1) resulted in release of methane and quantitative formation of [Cp*(PMe3)Rh(SiPh3)(CH2Cl2)]+BAr'4- (2). Subsequent addition of 1.0 equiv of MeCN to 2 caused immediate displacement of dichloromethane to form the eta1-nitrile adduct [Cp*(PMe3)Rh(SiPh3)(NCMe)]+BAr'4- (3). Upon standing at room-temperature overnight, complex 3 converted quantitatively to another product which has been characterized as the C-C activation product, [Cp*(PMe3)Rh(Me)(CNSiPh3)]+BAr'4- (5). Addition of other nitrile substrates (R-CN, R = Ph, (4-CF3)Ph, (4-MeO)Ph, iPr, tBu) to 2 also resulted in C-C activation of the R-CN bond to form [Cp*(PMe3)Rh(R)(CNSiPh3)]+BAr'4-. Evidence for an eta2-iminoacyl intermediate complex, [Cp*(PMe3)Rh(eta2-C(R)=N(SiPh3)]+BAr'4-, is also presented.

  DOI：

  10.1021/ja0255094
• 作为产物：
  描述：

  、 四(3,5-二(三氟甲基)苯基)硼酸钠 以 二氯甲烷 为溶剂， 以84%的产率得到[(C5(CH3)5)(P(CH3)3)Rh(CH3)(dichloromethane)][B(3,5-C6H3(CF3)2)4]
  参考文献：
  名称：

  [Cp*(PMe3)Rh(H)(H2)]+ 及其部分氘化和氚化同位素的合成和研究：氢化物/二氢结构的证据

  摘要：

  [Cp(PMe(3))Rh(Me)(CH(2)Cl(2))](+)BAr'(4)(-) (4, Ar' = 3,5-C(6)) 的氢解H(3)(CF(3))(2)) 在二氯甲烷中得到非经典的多氢化物复合物 [Cp*PMe(3))Rh(H)(H(2))](+)BAr'(4)(- ) (1)，在 (1)H NMR 光谱中的所有可接近温度下都表现出单一的氢化物共振。暴露 1 到 D(2) 或 T(2) 气体的解决方案导致氢化物站点中的部分同位素替换。1 作为氢化物/二氢复合物的配方基于 T(1) (T(1)(min) = 23 ms at 150 K, 500 MHz), J(HD) (ca. 10 Hz), and J(HT ) (ca. 70 Hz) 测量。氢化物与二氢位点交换的屏障 (Delta G(++)) 被确定为小于约。5 大卡/摩尔。使用 H(OEt(2))(2)BAr'(4) 质子化

  DOI：

  10.1021/ja0165990
• 作为试剂：
  描述：

  phenylphosphine-borane 在 bis(1,2-bis(diphenylphosphino)ethane)rhdium(I) chloride 、 [(C5(CH3)5)(P(CH3)3)Rh(CH3)(dichloromethane)][B(3,5-C6H3(CF3)2)4] 作用下， 生成
  参考文献：
  名称：

  催化可逆链转移脱氢聚合合成聚膦基硼烷嵌段共聚物

  摘要：

  多膦基硼烷的两亲嵌段共聚物 [H 2 BPPhH] 110 - b -[H 2 BP(n-hexyl)H] 11已通过前体单体 H 3的催化可逆链转移脱氢聚合的机制主导策略制备B ⋅ PRH 2（R=Ph，h-己基）。这些在 THF:己烷溶液中自组装形成纳米结构的棒状胶束，其形态可通过溶剂极性控制。

  DOI：

  10.1002/anie.202216106

文献信息

• Silicon−Hydrogen Bond Activation and Formation of Silane Complexes Using a Cationic Rhodium(III) Complex
  作者：Felicia L. Taw、Robert G. Bergman、Maurice Brookhart

  DOI：10.1021/om0341303

  日期：2004.2.1

  Addition of triphenylsilane, trimethylsilane, or triethylsilane to [Cp*(PMe3)Rh(Me)(CH2Cl2)]BAr‘4 (4), a cationic Rh(III) complex, resulted in Si−H bond activation and release of methane below −80 °C. The rare, nonclassical silane complexes [Cp*(PMe3)Rh((C6H4)(η2-HSiPh2))]BAr‘4 (6), [Cp*(PMe3)Rh(SiMe3)(η2-HSiMe3)]BAr‘4 (9), and [Cp*(PMe3)Rh(SiEt3)(η2-HSiEt3)]BAr‘4 (11) have been generated and characterized

  三苯基硅烷，三甲基硅烷，或三乙基甲硅烷来的另外的[Cp *（PME 3）的Rh（ME）（CH 2氯2）] BAR” 4（4），阳离子铑（III）络合物，导致Si-H键活化和低于-80°C释放甲烷。罕见，非经典硅烷络合物的[Cp *（PME 3）的Rh（（C 6 H ^ 4）（η 2 -HSiPh 2））] BAR” 4（6），的[Cp *（PME 3）的Rh（森达3）（ η 2 -HSiMe 3）] BAR” 4（9），和的[Cp *（PME 3）的Rh（SIET3）（η 2 -HSiEt 3）] BAR” 4（11）已经被产生并通过NMR光谱学。值得注意的是存在29个每个这些化合物和大的的氢化物共振的硅卫星1 Ĵ硅- ħ偶合常数（56-84赫兹），诊断η的存在的2 -硅烷配体。
• Aromatic and aldehyde carbon–hydrogen bond activation at cationic Rh(III) centers. Evaluation of electronic substituent effects on aldehyde binding and C–H oxidative addition
  作者：Britton K. Corkey、Felicia L. Taw、Robert G. Bergman、Maurice Brookhart

  DOI：10.1016/j.poly.2004.09.005

  日期：2004.11

  Cationic rhodium methyl complexes, [Cp-*(PMe3)Rh(Me)(CH2Cl2)]BAr4' (1) and [Cp-*(P(OMe)(3))Rh(Me)(CH2Cl2)]BAr4' (3), react with benzene to yield the corresponding phenyl complexes, [Cp-*(PMe3)Rh(Ph)(CH2Cl2)]BAr4' (6) and [Cp-*(P(OMe)(3))Rh(Ph)(CH2Cl2)]BAr4' (7). First-order rate constants observed in 1.1 M benzene in CD2Cl2 at 25 degreesC are (2.1 +/- 0.2) x 10(-5) s(-1) and (1.9 +/- 0.2) x 10(-5) s(-1), respectively. Reactions of 1 and 3 with p-X-substituted benzaldehydes (X = -CF3, -CH3, and -OMe) initially produce the sigma-aldehyde adducts, [Cp-*(L)Rh(Me)(p-XC6H4CHO)]BAr4' (L = PMe3 (15), P(OMe)(3) (16)). Exchange of free with bound aldehyde occurs via a dissociative process and quantitative NMR rate measurements show that complexes of 1 exchange faster than those of 3 and that less basic aldehydes exchange faster than more basic aldehydes (p-CF3C6H4CHO > p-CH3C6H4CHO > p-CH3OC6H4CHO). The aldehyde adducts undergo C-H bond activation to produce initially methane plus acyl aldehyde adducts, [Cp-*(L)Rh(C(O)C6H4X)(p - XC6H4CHO)]BAr4' (L = PMe3 (17), P(OMe)(3) (18)). Rates of C-H activation are correlated with aldehyde exchange rates; activation barriers of weakly bound aldehydes are lower than more strongly bound aldehydes. In the case of L = PMe3, decarbonylation of the aldehyde adducts occurs cleanly to form aryl carbonyl complexes, [Cp-*(PMe3)Rh(C6H4X)(CO)]BAr4'. For L = P(OMe)(3), decarbonylation is a more complicated process; some intermediates and products have been identified by NMR spectroscopy. (C) 2004 Elsevier Ltd. All rights reserved.