[Cr(CO)2(1,5,9-triphosphacyclododecane)Br]Br | 178988-41-5

• 英文名称: [Cr(CO)2(1,5,9-triphosphacyclododecane)Br]Br
• CAS: 178988-41-5
• 化学式: Br*C₁₁H₂₁BrCrO₂P₃
• 分子量: 490.012
• InChiKey: KKEFGKIFYOZOCC-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 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

• 作为产物：
  描述：

  tricarbonyl(1,5,9-triphosphacyclododecane)chromium 、 溴 以 not given 为溶剂， 生成 [Cr(CO)2(1,5,9-triphosphacyclododecane)Br]Br
  参考文献：
  名称：

  Stereoselective Synthesis of 1,5,9-Triphosphacyclododecane and Tertiary Derivatives

  摘要：

  Selective oxidation of Mo(CO)(3) complexes of tritertiary 1,5,9-triphosphacyclododecane macrocycles (R(3)L) by halogens (X(2) = Cl-2, Br-2, I-2) to Mo(II) triphospha macrocycle complexes of the type (R(3)L)Mo(CO)(2)X(2) [R = (CH3)(2)CH (2), (CH3)(3)SiCH2 (3), C2H5 (4), (CH3)(2)CHCH2 (5)] allows the high yield and stereoselective liberation of the corresponding tritertiary macrocycles [syn,syn-R(3)L, R = (CH3)(2)CH (6), (CH3)(3)SiCH2 (7), C2H5 (8), (CH3)(2)CHCH2 (9)] in good yield (75-80%) by digestion in strong base. This method fails for the parent trisecondary macrocycle (H(3)L) and also for the intermediate Mo(II) salts, [(R(3)L)Mo(CO)(3)X]A(-) [X = halide, A(-) = halide, BPh(4) (1)]. Addition of halogen to (H(3)L)Cr(CO)(3) gives rise to the new blue-violet complexes (H(3)L)Cr(CO)(2)X(2) [X = Cl-2 (11), Br-2 (12)]. Paramagnetic susceptibilities indicate that 11 and 12 are low-spin d(4) six coordinate dicarbonyl halo-halide complexes of the type [(H(3)L)Cr(CO)(2)X]X. In this case, the trisecondary 1,5,9-triphosphacyclododecane (H(3)L, 13) may be liberated stereoselectively and in reasonable yield (60-70%) from 11 or 12. The macrocycles may alternatively be liberated from the Mo(II) dihalo complexes by action of CN-. The free trisecondary macrocycle can be alkylated nonstereoselectively to give the tritertiary macrocycles [syn,-anti-R(3)L; R = CH3 (24), C2H5 (8b), (CH3)(3)C (25)]. The inversion of phosphorus in the syn,syn isomer 8 to its syn,anti analogue, 8b, was shown to be slow at 156 degrees C. Exhaustive oxidation of the Mo(0) macrocycle complexes with H2O2 Or O-3 results in liberation of the corresponding macrocycle trioxides in good yield. All free macrocycles (and oxides) have been characterized by spectroscopic methods and as the hydrochlorides for selected ligands.

  DOI：

  10.1021/ic960322x