H(BH3)cyclenPMo(CO)5 | 126369-02-6

• 英文名称: H(BH3)cyclenPMo(CO)5
• CAS: 126369-02-6
• 化学式: C₁₃H₂₀BMoN₄O₅P
• 分子量: 450.05
• InChiKey: MBPDPSVVKYXVKT-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  HcyclenPMo(CO)5 、 borane tetrahydrofuran 以 正己烷 为溶剂， 以79%的产率得到H(BH3)cyclenPMo(CO)5
  参考文献：
  名称：

  路易斯酸控制金属化环磷烷的互变异构

  摘要：

  HcyclenPMo（CO）5（2）物种包含具有P⋯N跨环相互作用的三角双锥体磷，它与HBF 4或Me 3 OBF 4反应并导致形成磷化物（R 4 P :-)加合物，而（2）与THF·BH 3（THF =四氢呋喃）的反应产生意外的膦加合物H（BH 3）cyclnP-Mo（CO）5（5），其X射线结构揭示了cyclnP的空前构象戒指。

  DOI：

  10.1039/c39890001538

文献信息

• Transition-metal-mediated reactions of cyclenphosphorane: synthesis and reactivity of HcyclenPMo(CO)5, a species with a transannular P---N interaction
  作者：Dilip V. Khasnis、Michael Lattman、Upali Siriwardane

  DOI：10.1021/om00051a023

  日期：1991.5

  The reaction of cyclenphosphorane (cyclenPH) with Mo(CO)6 in refluxing toluene yields HcyclenPMo(CO)5 (4), in which the phosphorus is bonded to the molybdenum. The geometry around phosphorus is best described as a trigonal bipyramid with two nitrogens and the molybdenum at the equatorial positions and two nitrogens at the axial positions. The N-H axial nitrogen interacts with the phosphorus through its lone pair of electrons in a transannular arrangement with a P---N distance of 2.356 (23) angstrom. Reactions of 4 with electrophiles occur for the most part at the secondary amine of the HcyclenP ligand, even though its lone pair is involved in the transannular interaction. Protonation with HBF4 yields [H2cyclenPMo(CO)5]BF4 (5), in which the phosphorous is pentacoordinate and both axial nitrogens are protonated, while treatment with THF-BH3 gives H(BH3)cyclenPMo(CO)5 (6), the borane adduct of a secondary amine. Reaction of 4 with CF3SO3CH3 in a 2:1 molar ratio yields two products, CH3cyclenPMo(CO)5 (7) and [H2cyclenPMo(CO)5]CF3SO3 (8). The former is the methyl analogue of the starting material 4, while the latter contains the same cation as 5. Treatment of 4 with DMAD results in addition of the N-H across the triple bond to give the enamine (cis-CH3O2CCH = CCO2CH3)cyclenPMo(CO)5 (9). X-ray data for 9: C17H23N4O9PMo, monoclinic, space group c2/c, a = 27.10 (3) angstrom, b = 12.063 (14) angstrom, c = 14.688 (10) angstrom, beta = 94.12 (7)-degrees, Z = 8, R = 0.029, R(w) = 0.028.