(Me5Cp)Hf(NMe2)3 | 923015-99-0

• 英文名称: (Me5Cp)Hf(NMe2)3
• CAS: 923015-99-0
• 化学式: C₁₆H₃₃HfN₃
• 分子量: 445.948
• InChiKey: GDCRNSOOPISGEV-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：

  (Me5Cp)Hf(NMe2)3 、 2-Oxazolamine, 4,5-dihydro-4,4-dimethyl-N-phenyl- 以 甲苯 为溶剂， 以50%的产率得到
  参考文献：
  名称：

  Chiral Alkoxide-Functionalized Guanidinates from Ring-Opening Rearrangement of Aminooxazolinate Complexes

  摘要：

  Treatment of Cp*M(NMe2)(3) (M = Zr, Hf) with both achiral and optically pure chiral aminooxazoline proligands HL yields metastable aminooxazolinate half-sandwich diamide complexes [Cp*ML(NMe2)(2)]. These species undergo clean rearrangement via oxazoline ring-opening to carbodiimides followed by amide migratory insertion. The chiral-at-metal products contain tridentate alkoxide-functionalized guanidinates, as confirmed by X-ray diffraction. In some of the chiral ligand systems, single diastereomer samples can be prepared, either by direct reaction or after recrystallization. As a result of the chelate structure, no thermal conversion between diastereomers is observed. A mechanism leading to the observed diastereoselection involving an intramolecular CH-pi interaction in the major product is proposed.

  DOI：

  10.1021/om0607649
• 作为产物：
  描述：

  五甲基环戊二烯基三氯化铪(IV) 、 lithium dimethylamide 以 甲苯 为溶剂， 以80%的产率得到(Me5Cp)Hf(NMe2)3
  参考文献：
  名称：

  Chiral Alkoxide-Functionalized Guanidinates from Ring-Opening Rearrangement of Aminooxazolinate Complexes

  摘要：

  Treatment of Cp*M(NMe2)(3) (M = Zr, Hf) with both achiral and optically pure chiral aminooxazoline proligands HL yields metastable aminooxazolinate half-sandwich diamide complexes [Cp*ML(NMe2)(2)]. These species undergo clean rearrangement via oxazoline ring-opening to carbodiimides followed by amide migratory insertion. The chiral-at-metal products contain tridentate alkoxide-functionalized guanidinates, as confirmed by X-ray diffraction. In some of the chiral ligand systems, single diastereomer samples can be prepared, either by direct reaction or after recrystallization. As a result of the chelate structure, no thermal conversion between diastereomers is observed. A mechanism leading to the observed diastereoselection involving an intramolecular CH-pi interaction in the major product is proposed.

  DOI：

  10.1021/om0607649

文献信息

• Half-Sandwich Zirconium and Hafnium Amidoborane Complexes: Precursors of Hydride Derivatives
  作者：Maider Greño、Adrián Pérez-Redondo、José Torrijos、Víctor Varela-Izquierdo、Carlos Yélamos

  DOI：10.1021/acs.inorgchem.3c02826

  日期：2024.4.15

  or tris(dimethylamido) [M(η5-C5Me5)(NMe2)3] derivatives react with NHMe2BH3 (≥3 equiv) to afford bis(dimethylamidoborane) hydride complexes [M(η5-C5Me5)H(NMe2BH3)2] (M = Zr (3), Hf (4)) via thermally unstable [M(η5-C5Me5)(NMe2BH3)3] species. The reaction of [M(η5-C5Me5)(NMe2)3] and NH2tBuBH3 (≥4 equiv) affords analogous mixed amidoborane hydride derivatives [M(η5-C5Me5)H(NHtBuBH3)(NMe2BH3)] (M = Zr (5)

  在单（五甲基环戊二烯基）金属烷基和酰胺衍生物与胺-硼烷 NHR2BH3 （R2 = H2， Me2， HtBu） 的化学计量反应中分离出具有酰胺硼烷和氢化物配体的半夹心锆 （IV） 和铪 （IV） 配合物。用 NH3BH3（3 当量）处理三（三甲基硅烷基甲基）络合物 [M（η5-C 5Me5）（CH2SiMe3）3] 得到七配位物质 [M（η5-C 5Me5）（NH2BH3）3]（M = Zr （1），Hf （2）），具有三个 κ2N，H-NH 2BH3 配体。三（新叶）[M（η5-C 5Me5）（CH2CMe2Ph）3] 或三（二甲酰胺基）[M（η5-C 5Me5）（NMe2）3] 衍生物与 NHMe2BH3（≥3 当量）反应得到双（二甲基酰胺硼烷）氢化物络合物 [M（η5-C 5Me5）H（NMe2BH3）2] （M = Zr （3）， Hf （4）） 通过热不稳定的 [M（η5-C 5Me5）（NMe2BH3）3]