tricarbonyl[1,5,9-tris(isopropyl)-1,5,9-triphosphacyclododecane]molybdenum(0) | 163164-82-7

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: tricarbonyl[1,5,9-tris(isopropyl)-1,5,9-triphosphacyclododecane]molybdenum(0)
• 英文别名: Mo(CO)3(1,5,9-triisopropyl-1,5,9-triphosphacyclododecane)；Carbon monoxide;molybdenum;1,5,9-tri(propan-2-yl)-1,5,9-triphosphacyclododecane
• CAS: 163164-82-7
• 化学式: C₂₁H₃₉MoO₃P₃
• 分子量: 528.4
• InChiKey: ZRAVPTQCMDBFJI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.73
• 重原子数：
  28
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tricarbonyl[1,5,9-tris(isopropyl)-1,5,9-triphosphacyclododecane]molybdenum(0) 在 Br₂ 作用下， 以 二氯甲烷 为溶剂， 以75%的产率得到[MoBr(CO)3(1,5,9-tris(isopropyl)-1,5,9-triphosphacyclododecane)]Br
  参考文献：
  名称：

  二价第6族过渡金属的三磷大环配合物；溴三羰基-[1,5,9-三（异丙基）-1,5,9-三磷环十二烷]-四苯基硼酸钼（II）的晶体结构

  摘要：

  通过将卤素氧化添加到1,5,9-三磷环十二烷和三叔膦类似物的三羰基钼和钨三羰基钨配合物中，制得了钼（II）和钨（II）的新三磷杂环化合物。这些大环配合物的行为与先前报道的单齿叔膦的实施例相似，金属（0）前体最初生成含[M（CO）3 X（L）] +的七配位盐。阳离子（L =三齿三磷酰胺大分子）与卤化物阴离子，可以与其他抗衡离子交换。七坐标络合物在溶液中都是可流动的，并产生了随温度变化的NMR光谱。在低温极限下，在所有新配合物的31 P NMR光谱中观察到AB 2型。所有的盐都缓慢地转化为中性的七坐标二羰基二卤代配合物[M（CO）2 X 2（L）]。这些是除最初制备大环配体的金属（0）三羰基模板配合物以外的1,5,9-三磷环十二烷族金属配合物的第一个实例。

  DOI：

  10.1039/dt9950004091
• 作为产物：
  描述：

  [MoI(CO)3(1,5,9-tris(isopropyl)-1,5,9-triphosphacyclododecane)]BPh4 以 not given 为溶剂， 生成 tricarbonyl[1,5,9-tris(isopropyl)-1,5,9-triphosphacyclododecane]molybdenum(0)
  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

文献信息

• 1,5,9-Triphosphacyclododecane complexes of molybdenum and tungsten; crystal structure of tricarbonyl[1,5,9-tris(isopropyl)-1,5,9-triphosphacyclododecane]-molybdenum(0)
  作者：Simon J. Coles、Peter G. Edwards、James S. Fleming、Michael B. Hursthouse

  DOI：10.1039/dt9950001139

  日期：——

  The first tritertiary 1,5,9-triphosphacyclododecane ligand complexes of molybdenum were prepared from the trisecondary 1,5,9-triphosphacyclododecane precursor. The tungsten trisecondary 1,5,9-triphosphacyclododecane analogue has been synthesised and also serves as an intermediate to the first tungsten complexes of the tertiary phosphine macrocyclic ligands. The synthetic routes are general and allow

  钼的第一三级1,5,9-三磷环十二烷配体配合物是从三级1,5,9-三磷环十二烷前体制备的。钨三仲1,5,9-三磷环十二烷类似物已经合成，并且还用作叔膦大环配体的第一个钨配合物的中间体。合成途径是通用的，并允许获得一系列在磷上具有烷基，ω-氨基烷基和烯基官能团的大环三膦。所有化合物均已在光谱上进行了表征，并在结构上表征了三异丙基钼衍生物[Mo（CO）3 环-（Pr i PC 3 H 6）3 }]。