[N,o-C-(N-benzylidenebenzylaminato)]hydrido(acetone)bis(triphenylphosphine)rhodium(III) hexafluorophosphate | 850199-97-2

• 英文名称: [N,o-C-(N-benzylidenebenzylaminato)]hydrido(acetone)bis(triphenylphosphine)rhodium(III) hexafluorophosphate
• CAS: 850199-97-2
• 化学式: C₅₃H₄₉NOP₂Rh*F₆P
• 分子量: 1025.8
• InChiKey: YJJSXGXXTNEHSN-BNTVHEPCSA-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：

  氘代甲醇 、 [N,o-C-(N-benzylidenebenzylaminato)]hydrido(acetone)bis(triphenylphosphine)rhodium(III) hexafluorophosphate 以 氘代甲醇 为溶剂， 生成 [N,o-C-(N-benzylidenebenzylaminato)]hydrido(methanol-d4)bis(triphenylphosphine)rhodium(III) hexafluorophosphate
  参考文献：
  名称：

  Rhodium(III)-Cyclometalated-Imine Complexes:  Solution Behavior and Reactivity with Molecular Hydrogen

  摘要：

  Acetone solutions of cis, trans, cis-[Rh(H)(2)(PPh3)(2)(acetone)(2)] PF6 and cis-[Rh(PPh3)(2)(acetone)(2)]PF6 react with the imines RN=CR '(R ''), where R = PhCH2, Ph, or C6H11; R '= H or Me; and R '' = Ph or P-OMe-C6H4, to form orthometalated complexes exemplified by [Rh(H){RN= CR '(o-C6H4)}(PPh3)(2)(acetone)]PF6 that are generally characterized spectroscopically, and in one case (where R = PhCH2, R ' = Me, and R '' = p-OMe-C6H4) by X-ray crystallography. These complexes maintain their integrity in acetone solution and show no reaction toward 1 atm H-2 at ambient conditions. In MeOH, the complexes in which R ' = Me simply change to the corresponding MeOH derivative, but when R ' = H they are partially converted to the non-orthometalated, eta(1)-N-imine species [Rh(PPh3)(2)(RN=CHR '')(MeOH)]PF6 (I), and in MeOH, stoichiometric hydrogenation of the imine to the corresponding amine occurs via I. We have shown recently (Inorg. Chem. 2004, 43, 4820) that the catalyzed hydrogenation of PhCH2N=C(H)Ph to dibenzylamine using cis, trans, cis- [Rh(H)(2)(PPh3)(2)(MeOH)(2)] PF6 as catalyst precursor in MeOH proceeds via a cationic Rh-(eta(1)-N-imine)(amine) intermediate (II), analogous to I but with the MeOH replaced by the amine that is formed via hydrolysis of the imine by the presence of adventitious water. Intermediate I (R = PhCH2, R '' = Ph) is shown to be somewhat less active than II toward H-2, but both intermediates provide viable pathways for hydrogenation of the imine. The orthometalated imine-amine complex [Rh(H){PhCH2N=C(Me)(o-C6H4)}(PPh3)(2)(NH2CH2Ph)]PF6, where the benzylamine comes from imine hydrolysis, is also isolated and characterized crystallographically.

  DOI：

  10.1021/om049121o
• 作为产物：
  描述：

  cis-[Rh(PPh3)2(acetone)2]PF6 、 N-苄烯丁胺 、 丙酮 以 丙酮 为溶剂， 生成 [N,o-C-(N-benzylidenebenzylaminato)]hydrido(acetone)bis(triphenylphosphine)rhodium(III) hexafluorophosphate
  参考文献：
  名称：

  Rhodium(III)-Cyclometalated-Imine Complexes:  Solution Behavior and Reactivity with Molecular Hydrogen

  摘要：

  Acetone solutions of cis, trans, cis-[Rh(H)(2)(PPh3)(2)(acetone)(2)] PF6 and cis-[Rh(PPh3)(2)(acetone)(2)]PF6 react with the imines RN=CR '(R ''), where R = PhCH2, Ph, or C6H11; R '= H or Me; and R '' = Ph or P-OMe-C6H4, to form orthometalated complexes exemplified by [Rh(H){RN= CR '(o-C6H4)}(PPh3)(2)(acetone)]PF6 that are generally characterized spectroscopically, and in one case (where R = PhCH2, R ' = Me, and R '' = p-OMe-C6H4) by X-ray crystallography. These complexes maintain their integrity in acetone solution and show no reaction toward 1 atm H-2 at ambient conditions. In MeOH, the complexes in which R ' = Me simply change to the corresponding MeOH derivative, but when R ' = H they are partially converted to the non-orthometalated, eta(1)-N-imine species [Rh(PPh3)(2)(RN=CHR '')(MeOH)]PF6 (I), and in MeOH, stoichiometric hydrogenation of the imine to the corresponding amine occurs via I. We have shown recently (Inorg. Chem. 2004, 43, 4820) that the catalyzed hydrogenation of PhCH2N=C(H)Ph to dibenzylamine using cis, trans, cis- [Rh(H)(2)(PPh3)(2)(MeOH)(2)] PF6 as catalyst precursor in MeOH proceeds via a cationic Rh-(eta(1)-N-imine)(amine) intermediate (II), analogous to I but with the MeOH replaced by the amine that is formed via hydrolysis of the imine by the presence of adventitious water. Intermediate I (R = PhCH2, R '' = Ph) is shown to be somewhat less active than II toward H-2, but both intermediates provide viable pathways for hydrogenation of the imine. The orthometalated imine-amine complex [Rh(H){PhCH2N=C(Me)(o-C6H4)}(PPh3)(2)(NH2CH2Ph)]PF6, where the benzylamine comes from imine hydrolysis, is also isolated and characterized crystallographically.

  DOI：

  10.1021/om049121o