rhenium(N(C6H5)2)(CO)3(2,2'-bipyridine) | 431875-01-3

• 英文名称: rhenium(N(C6H5)2)(CO)3(2,2'-bipyridine)
• 英文别名: fac-tricarbonyl(2,2'-bipyridine)(diphenylamido)rhenium(I)
• CAS: 431875-01-3
• 化学式: C₂₅H₁₈N₃O₃Re
• 分子量: 594.643
• InChiKey: XFXRVPAGCAQWQG-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：

  三氟甲烷磺酸甲酯 、 rhenium(N(C6H5)2)(CO)3(2,2'-bipyridine) 以 二氯甲烷-D2 为溶剂， 生成 (2,2'-bipyridine)tricarbonylrhenium trifluoromethanesulfonate
  参考文献：
  名称：

  New Octahedral Rhenium(I) Tricarbonyl Amido Complexes

  摘要：

  Several new Re(I) octahedral amido complexes fac-[Re(NRR')(CO)(3)(N-N)1 (R = aryl; R' = H, aryl; N-N = 2,2-bipyridine, bipy; 1,10-phenanthroline, phen) have been synthesized either by reaction of [Re(OTf)(CO)(3)(N-N)] precursors with potassium amides or by deprotonation of [Re(NH2Ar)(CO)(3)(N-N)OTf compounds, in turn obtained by reaction of [Re(OTf)(CO)(3)(N-N)] compounds with amines. The structure of the amido complexes [Re(NHPh)(CO)3(bipy)] (5) and [Re(NPh2)(CO)(3)(bipy)] (6) have been determined by single-crystal X-ray diffraction. The results, coupled with the solution NMR behavior of the complexes, indicate that the delocalization of the nitrogen lone pair of the amido group involves mainly the N-aryl bonds. Amido complexes [Re(NEp-Tol)(CO)(3)(N-N)] (4a,b) (p-Tol = 4-methylphenyl) react with 4-ethylphenol, with ethanothiol, and with diphenylphosphine to give the complexes [Re(OC6H4-4-C2H5)(CO)(3)(bipy)] (8), [Re(SCH2CH3)(CO)(3)(bipy)] (9), and [Re(PPh2)(CO)(3)(N-N)] (10a,b). The structure of the diphenylphosphido complex [Re(Ph-2)(CO)(3)(phen)] (10b), determined by X-ray diffraction, was compared with the structure of the homologous diphenylamido complex 6. The different geometries (pyramidal phosphorus and planar amido nitrogen) correlate with the higher nucleophilicity of the phosphido complex.

  DOI：

  10.1021/om0110383
• 作为产物：
  描述：

  二苯胺 、 (2,2'-bipyridine)tricarbonylrhenium trifluoromethanesulfonate 在 KN(SiMe₃)2 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 以72%的产率得到rhenium(N(C6H5)2)(CO)3(2,2'-bipyridine)
  参考文献：
  名称：

  New Octahedral Rhenium(I) Tricarbonyl Amido Complexes

  摘要：

  Several new Re(I) octahedral amido complexes fac-[Re(NRR')(CO)(3)(N-N)1 (R = aryl; R' = H, aryl; N-N = 2,2-bipyridine, bipy; 1,10-phenanthroline, phen) have been synthesized either by reaction of [Re(OTf)(CO)(3)(N-N)] precursors with potassium amides or by deprotonation of [Re(NH2Ar)(CO)(3)(N-N)OTf compounds, in turn obtained by reaction of [Re(OTf)(CO)(3)(N-N)] compounds with amines. The structure of the amido complexes [Re(NHPh)(CO)3(bipy)] (5) and [Re(NPh2)(CO)(3)(bipy)] (6) have been determined by single-crystal X-ray diffraction. The results, coupled with the solution NMR behavior of the complexes, indicate that the delocalization of the nitrogen lone pair of the amido group involves mainly the N-aryl bonds. Amido complexes [Re(NEp-Tol)(CO)(3)(N-N)] (4a,b) (p-Tol = 4-methylphenyl) react with 4-ethylphenol, with ethanothiol, and with diphenylphosphine to give the complexes [Re(OC6H4-4-C2H5)(CO)(3)(bipy)] (8), [Re(SCH2CH3)(CO)(3)(bipy)] (9), and [Re(PPh2)(CO)(3)(N-N)] (10a,b). The structure of the diphenylphosphido complex [Re(Ph-2)(CO)(3)(phen)] (10b), determined by X-ray diffraction, was compared with the structure of the homologous diphenylamido complex 6. The different geometries (pyramidal phosphorus and planar amido nitrogen) correlate with the higher nucleophilicity of the phosphido complex.

  DOI：

  10.1021/om0110383

文献信息

• Different sites of insertion in the reaction of isocyanates with [Re(N(R)Ar)(CO)₃(bipy)] (R = H or Me): N–H vs. Re–N
  作者：Eva Hevia、Julio Pérez、Víctor Riera、Daniel Miguel

  DOI：10.1039/b203261a

  日期：——

  The reactions of isocyanates with [Re(N(R)Ar)(CO)3(bipy)] complexes lead to R′NCO insertion into the Re–N bond (for R = Me) or the N–H bond (R = H)

  异氰酸酯与[Re(N(R)Ar)(CO)3(bipy)]复合物的反应会导致 Râ²NCO 插入 ReâN 键（R = Me）或 NâH 键（R = H）。