(3,5,8-triaza-1-phosphaadamantane)(triisopropyl phosphite)Cr(CO)4 | 134132-39-1

• 英文名称: (3,5,8-triaza-1-phosphaadamantane)(triisopropyl phosphite)Cr(CO)4
• CAS: 134132-39-1
• 化学式: C₁₉H₃₃CrN₃O₇P₂
• 分子量: 529.43
• InChiKey: JAZJDIGATSDQQP-UHFFFAOYSA-N

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：

  cis-(piperidine)(triisopropyl phosphite)Cr(CO)4 、 1,3,5-三氮杂-7-磷杂金刚烷 以 四氢呋喃 为溶剂， 生成 (3,5,8-triaza-1-phosphaadamantane)(triisopropyl phosphite)Cr(CO)4
  参考文献：
  名称：

  八面体金属羰基。76.顺式（pip）（L）Cr（CO）4复合物的配体交换研究（pip =哌啶； L = Lewis碱）

  摘要：

  A series of cis-(pip)(L)Cr(CO)4 complexes (pip = piperidine; L = P(OMe)3, P(OEt)3, P(O-i-Pr)3, P(OPh)3, P(OCH2)3CCH3, PPh3, P(CH2)3N3C3H6), potential precursors for the creation of [(L)Cr(CO)4] intermediates via flash photolysis, have been synthesized. The complexes react thermally in chlorobenzene (= CB) with L' (= P(OMe)3, P(OEt)3, P(O-i-Pr)3, P(OPh)3, P(OCH2)3CCH3, PPh3, P(n-Bu)3) to afford cis- and trans-(L)(L')Cr(CO)4 products according to a mechanism that kinetics data indicate to involve reversible dissociation of pip from cis-(pip)(L)Cr(CO)4 and competition between pip and L' for the cis-[(L)Cr(CO)4] intermediates thus produced. Intramolecular isomerization follows, affording largely trans-(L')(L)Cr(CO)4, where both L and L' are phosphines or are phosphites, but also substantial quantities of the cis isomer for ''mixed'' complexes containing one phosphine and one phosphite ligand. This observation is attributed to intramolecular hydrogen bonding (P-O..H-C-P) in the mixed complexes. Where the L ligands are phosphites, rates of dissociation of pip from cis-(pip)(L)Cr(CO)4 complexes increase with increasing steric bulk of L; the [(L)Cr(CO)5] intermediates produced upon Cr-pip bond breaking show little discriminating ability among incoming L'. The rate of pip dissociation from cis-(pip)(P(CH2)3N3C3H6)Cr(CO)4 at 31.1 degrees-C is 137 (2) times faster than that for cis-(pip)(P(OCH2)3CCH3)Cr(CO)4, in which L is sterically similar. This rate enhancement arises from a lack of intramolecular (N-H..O-P) hydrogen bonding between pip and L in the latter complex, which is present in the former. Activation energies suggest the strength of the hydrogen bond to be ca. 5 kcal/mol. These data suggest that the enthalpy of activation for Cr-pip bond dissociation closely approximates and represents an upper limit for the Cr-pip bond dissociation energy in this complex.

  DOI：

  10.1021/om00052a031