PhC(N2)Li | 135923-54-5

• 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: PhC(N2)Li
• CAS: 135923-54-5
• 化学式: C₇H₅LiN₂
• 分子量: 124.071
• InChiKey: FNFBQIAEDWTFNM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.74
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  5.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  PhC(N2)Li 、 [PtCl(C6H3(CH2P(iPr)2)2)] 以 四氢呋喃 为溶剂， 以80%的产率得到(PCP)Pt[C(N2)Ph]
  参考文献：
  名称：

  C-Metalated Diazoalkane Complexes of Platinum Based on PCP- and PCN-Type Ligands

  摘要：

  A series of the first C-metalated diazoalkane complexes of Pt, based on pincer-type PCN and PCP ligands (PCP = C6H3[CH2P(iPr)(2)](2); PCN = C6H3[CH2P(tBu)(2)](CH2)(2)N(CH3)(2)), with the general formula (PCX)Pt[C(N-2)RI (2, X = N, R = Ph; 3, X = N, R = SiMe3; 5, X = P, R = Ph) were prepared via direct nucleophilic attack of RCN2-Li+ at the metal center. These remarkably stable complexes were characterized by H-1, P-31{H-1}, and C-13 NMR and IR spectroscopy. Complex 2 was also characterized by single-crystal X-ray crystallography. Reactions of the C-metalated diazoalkane Pt complexes with Cu(I) (reported to catalyze decomposition of diazoalkanes) were strongly influenced by the nature of the pincer ligand. Bimolecular coupling to generate diphenylacetylene and (PCP)Pt-OTf (6) was observed in the case of the rigid PCP-based complex 5, while the hemilabile PCN-based complex 2 was converted to an ylide-bridged dimeric structure, the formation of which was promoted by the decoordination of the ligand amine arm. In addition, formation of the stable metalsubstituted azine-type binuclear complex 10, generated by reaction of 2 with Rh-2(OAc)(4), is described.

  DOI：

  10.1021/om050637x

文献信息

• C-Metalated Diazoalkane Complexes of Platinum Based on PCP- and PCN-Type Ligands
  作者：Elena Poverenov、Gregory Leitus、Linda J. W. Shimon、David Milstein

  DOI：10.1021/om050637x

  日期：2005.11.1

  A series of the first C-metalated diazoalkane complexes of Pt, based on pincer-type PCN and PCP ligands (PCP = C6H3[CH2P(iPr)(2)](2); PCN = C6H3[CH2P(tBu)(2)](CH2)(2)N(CH3)(2)), with the general formula (PCX)Pt[C(N-2)RI (2, X = N, R = Ph; 3, X = N, R = SiMe3; 5, X = P, R = Ph) were prepared via direct nucleophilic attack of RCN2-Li+ at the metal center. These remarkably stable complexes were characterized by H-1, P-31H-1}, and C-13 NMR and IR spectroscopy. Complex 2 was also characterized by single-crystal X-ray crystallography. Reactions of the C-metalated diazoalkane Pt complexes with Cu(I) (reported to catalyze decomposition of diazoalkanes) were strongly influenced by the nature of the pincer ligand. Bimolecular coupling to generate diphenylacetylene and (PCP)Pt-OTf (6) was observed in the case of the rigid PCP-based complex 5, while the hemilabile PCN-based complex 2 was converted to an ylide-bridged dimeric structure, the formation of which was promoted by the decoordination of the ligand amine arm. In addition, formation of the stable metalsubstituted azine-type binuclear complex 10, generated by reaction of 2 with Rh-2(OAc)(4), is described.