[(C5(CH3)5)(P(CH3)3)Rh(Si(C6H5)3)(η1-NCCH3)][B(3,5-C6H3(CF3)2)4] | 431882-05-2

• 英文名称: [(C5(CH3)5)(P(CH3)3)Rh(Si(C6H5)3)(η1-NCCH3)][B(3,5-C6H3(CF3)2)4]
• CAS: 431882-05-2
• 化学式: C₃₂H₁₂BF₂₄*C₃₃H₄₂NPRhSi
• 分子量: 1477.89
• InChiKey: IHXVYDNSCONGEI-UHFFFAOYSA-N

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：

  [(C5(CH3)5)(P(CH3)3)Rh(Si(C6H5)3)(η1-NCCH3)][B(3,5-C6H3(CF3)2)4] 、 乙腈 以 not given 为溶剂， 以99%的产率得到[(C5(CH3)5)(P(CH3)3)Rh(CH3)(CNSi(C6H5)3)][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：

  [(C5(CH3)5)(P(CH3)3)Rh(Si(C6H5)3)(dichloromethane)][B(3,5-C6H3(CF3)2)4] 、 乙腈 以 二氯甲烷 为溶剂， 生成 [(C5(CH3)5)(P(CH3)3)Rh(Si(C6H5)3)(η1-NCCH3)][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