[(2,6-bis(di-tert-butyl phosphino methyl)pyridine)Rh(acetone)]BF4 | 1048014-73-8

• 英文名称: [(2,6-bis(di-tert-butyl phosphino methyl)pyridine)Rh(acetone)]BF4
• 英文别名: [(2,6-bis(di-tert-butylphosphinomethyl)pyridine)Rh(acetone)][BF4]
• CAS: 1048014-73-8
• 化学式: BF₄*C₂₆H₄₉NOP₂Rh
• 分子量: 643.339
• InChiKey: RBOXSLZYPLOGBN-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：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [(2,6-bis(di-tert-butyl phosphino methyl)pyridine)Rh(acetone)]BF4 、 三乙基膦 以 丙酮 为溶剂， 生成 [(2,6-bis(di-tert-butyl phosphino methyl)pyridine)Rh(PEt3)]BF4
  参考文献：
  名称：

  Mononuclear Rh(II) PNP-Type Complexes. Structure and Reactivity

  摘要：

  The Rh(II) mononuclear complexes [((PNPBu)-Bu-t)RhCl][BF4] (2), [((PNPBu)-Bu-t)Rh(OC(O)CF3)][OC(O)CF3] (4), and [(PNPt-Bu)Rh(acetone)][BF4](2) (6) were synthesized by oxidation of the corresponding Rh(l) analogs with silver salts. On the other hand, treatment of ((PNPBu)-Bu-t)RhCl with AgOC(O)CF3 led only to chloride abstraction, with no oxidation. 2 and 6 were characterized by X-ray diffraction, EPR, cyclic voltammetry, and dipole moment measurements. 2 and 6 react with NO gas to give the diamagnetic complexes [((PNPBu)-Bu-t)Rh(NO)Cl][BF4] (7) and [((PNPBu)-Bu-t)Rh(NO)(acetone)][BF4](2) (8) respectively. 6 is reduced to Rh(I) in the presence of phosphines, CO, or isonitriles to give the Rh(l) complexes [((PNPBu)-Bu-t)Rh(PR3)][BF4] (11, 12) (R = Et, Ph), [((PNPBu)-Bu-t)Rh(CO)][BF4] (13) and [((PNPBu)-Bu-t)Rh(L)][BF4] (15, 16) (L = tert-butyl isonitrile or 2,6-dimethylphenyl isonitrile), respectively. On the other hand, 2 disproportionates to Rh(I) and Rh(III) complexes in the presence of acetonitrile, isonitriles, or CO; 2 is also reduced by triethylphosphine and water to Rh(I) complexes [((PNPBu)-Bu-t)RhCl] (1) and [((PNPBu)-Bu-t)Rh(PEt3)][BF4] (11). When triphenylphosphine and water are used, the reduced Rh(I) complex reacts with a proton, which is formed in the redox reaction, to give a Rh(III) complex with a coordinated BF4, [((PNPBu)-Bu-t)Rh(Cl)(H)(BF4)] (9).

  DOI：

  10.1021/ic701044b
• 作为产物：
  描述：

  2,6-双(二叔丁基膦基甲基)吡啶 、 以 丙酮 为溶剂， 以95%的产率得到[(2,6-bis(di-tert-butyl phosphino methyl)pyridine)Rh(acetone)]BF4
  参考文献：
  名称：

  Mononuclear Rh(II) PNP-Type Complexes. Structure and Reactivity

  摘要：

  The Rh(II) mononuclear complexes [((PNPBu)-Bu-t)RhCl][BF4] (2), [((PNPBu)-Bu-t)Rh(OC(O)CF3)][OC(O)CF3] (4), and [(PNPt-Bu)Rh(acetone)][BF4](2) (6) were synthesized by oxidation of the corresponding Rh(l) analogs with silver salts. On the other hand, treatment of ((PNPBu)-Bu-t)RhCl with AgOC(O)CF3 led only to chloride abstraction, with no oxidation. 2 and 6 were characterized by X-ray diffraction, EPR, cyclic voltammetry, and dipole moment measurements. 2 and 6 react with NO gas to give the diamagnetic complexes [((PNPBu)-Bu-t)Rh(NO)Cl][BF4] (7) and [((PNPBu)-Bu-t)Rh(NO)(acetone)][BF4](2) (8) respectively. 6 is reduced to Rh(I) in the presence of phosphines, CO, or isonitriles to give the Rh(l) complexes [((PNPBu)-Bu-t)Rh(PR3)][BF4] (11, 12) (R = Et, Ph), [((PNPBu)-Bu-t)Rh(CO)][BF4] (13) and [((PNPBu)-Bu-t)Rh(L)][BF4] (15, 16) (L = tert-butyl isonitrile or 2,6-dimethylphenyl isonitrile), respectively. On the other hand, 2 disproportionates to Rh(I) and Rh(III) complexes in the presence of acetonitrile, isonitriles, or CO; 2 is also reduced by triethylphosphine and water to Rh(I) complexes [((PNPBu)-Bu-t)RhCl] (1) and [((PNPBu)-Bu-t)Rh(PEt3)][BF4] (11). When triphenylphosphine and water are used, the reduced Rh(I) complex reacts with a proton, which is formed in the redox reaction, to give a Rh(III) complex with a coordinated BF4, [((PNPBu)-Bu-t)Rh(Cl)(H)(BF4)] (9).

  DOI：

  10.1021/ic701044b

文献信息

• Competitive C−I versus C−CN Reductive Elimination from a Rh^III Complex. Selectivity is Controlled by the Solvent
  作者：Moran Feller、Mark A. Iron、Linda J. W. Shimon、Yael Diskin-Posner、Gregory Leitus、David Milstein

  DOI：10.1021/ja8046798

  日期：2008.11.5

  forming an iodo RhI complex [(PNP)RhI] 9. Reaction of 2 with ethyl iodide in aprotic solvents gave the corresponding isonitrile complex, while in protic solvents no reactivity was observed. The selectivity of this reaction is likely due to a hydrogen bond between the cyano ligand and the protic solvent, as observed by X-ray diffraction, which retards electrophilic attack on this ligand.

  RhIII 复合物 [(PNP)Rh(CN)(CH3)][I] 5 是通过将碘甲烷氧化加成到 [(PNP)Rh(CN)] 2 上获得的，它通过两种途径选择性地反应： 在非质子溶剂中 CI 还原消除甲基碘，然后发生对氰基配体的亲电攻击，得到甲基异腈 RhI 复合物 [(PNP)Rh(CN )][I] 3，而在质子溶剂 CC 中，乙腈发生还原消除，形成碘RhI 复合物 [(PNP)RhI] 9. 2 与碘乙烷在非质子溶剂中反应得到相应的异腈复合物，而在质子溶剂中未观察到反应性。该反应的选择性很可能是由于氰基配体和质子溶剂之间的氢键，如 X 射线衍射所观察到的，这阻碍了对该配体的亲电攻击。